US20260003276A1 - Photosensitive resin composition, cured substance, laminate, manufacturing method for cured substance, manufacturing method for laminate, manufacturing method for semiconductor device, and semiconductor device - Google Patents

Photosensitive resin composition, cured substance, laminate, manufacturing method for cured substance, manufacturing method for laminate, manufacturing method for semiconductor device, and semiconductor device

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Publication number
US20260003276A1
US20260003276A1 US19/320,385 US202519320385A US2026003276A1 US 20260003276 A1 US20260003276 A1 US 20260003276A1 US 202519320385 A US202519320385 A US 202519320385A US 2026003276 A1 US2026003276 A1 US 2026003276A1
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United States
Prior art keywords
group
formula
resin composition
photosensitive resin
compound
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Pending
Application number
US19/320,385
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English (en)
Inventor
Atsuyasu NOZAKI
Kazuya Oota
Yuta Yamakawa
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Fujifilm Corp
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Fujifilm Corp
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Filing date
Publication date
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Publication of US20260003276A1 publication Critical patent/US20260003276A1/en
Pending legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0048—Photosensitive materials characterised by the solvents or agents facilitating spreading, e.g. tensio-active agents
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/022—Quinonediazides
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/022—Quinonediazides
    • G03F7/023—Macromolecular quinonediazides; Macromolecular additives, e.g. binders
    • G03F7/0233—Macromolecular quinonediazides; Macromolecular additives, e.g. binders characterised by the polymeric binders or the macromolecular additives other than the macromolecular quinonediazides
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/037—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polyamides or polyimides
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G03F7/0387—Polyamides or polyimides
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G03F7/0388—Macromolecular compounds which are rendered insoluble or differentially wettable with ethylenic or acetylenic bands in the side chains of the photopolymer
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/16—Coating processes; Apparatus therefor
    • G03F7/168—Finishing the coated layer, e.g. drying, baking, soaking
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20—Exposure; Apparatus therefor
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/38—Treatment before imagewise removal, e.g. prebaking
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/40—Treatment after imagewise removal, e.g. baking
    • H01L21/0275—
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P76/00—Manufacture or treatment of masks on semiconductor bodies, e.g. by lithography or photolithography
    • H10P76/20—Manufacture or treatment of masks on semiconductor bodies, e.g. by lithography or photolithography of masks comprising organic materials
    • H10P76/204—Manufacture or treatment of masks on semiconductor bodies, e.g. by lithography or photolithography of masks comprising organic materials of organic photoresist masks
    • H10P76/2041—Photolithographic processes
    • H10P76/2042—Photolithographic processes using lasers

Definitions

  • the present invention relates to a photosensitive resin composition, a cured substance, a laminate, a manufacturing method for a cured substance, a manufacturing method for a laminate, a manufacturing method for a semiconductor device, and a semiconductor device.
  • use applications of the above-described resin material are not particularly limited, and examples thereof in a semiconductor device for mounting include the use as a material of an insulating film or sealing material, or as a protective film.
  • a resin can also be used as a base film, a cover lay, or the like for a flexible substrate.
  • the resin composition can be applied by a publicly known coating method or the like, it can be said that the resin composition is excellent in the manufacturing adaptability, for example, a high degree of freedom in designing the shape, size, application position of the resin composition to be applied during application. From the viewpoint of such excellent manufacturing adaptability, the industrial application and development of the above-described resin composition are expected increasingly.
  • WO2020/255859A describes a curable resin composition containing at least one resin selected from the group consisting of a polyimide and a polyimide precursor, which has a polyalkyleneoxy group and a polymerizable group, a polymerization initiator, a polymerizable compound, and a solvent.
  • WO2021/039782A describes a curable resin composition containing a resin having a repeating unit with a specific structure and a solvent.
  • An object of the present invention is to provide a photosensitive resin composition having excellent resolution in a case of forming a pattern of a cured substance, a cured substance obtained by curing the composition, a laminate including the cured substance, a manufacturing method for a cured substance, a manufacturing method for a laminate, a manufacturing method for a semiconductor device including a manufacturing method for a cured substance, and a semiconductor device including a cured substance.
  • a photosensitive resin composition comprising:
  • a photosensitive resin composition comprising:
  • the dissolution rate of the film in cyclopentanone is 0.1 ⁇ m/sec or more and less than 0.6 ⁇ m/sec.
  • Condition (2) a change rate in film thickness before and after immersion is less than 20% after the cured substance is immersed at 75° C. for 15 minutes in a mixture of dimethyl sulfoxide and a 25% by mass aqueous tetramethylammonium hydroxide solution in 90:10 (mass ratio).
  • a coefficient of thermal expansion of the cured substance in a temperature range of 25° C. to 125° C. is more than 20 ppm/° C. and 75 ppm/° C. or less.
  • ⁇ 21> A cured substance obtained by curing the photosensitive resin composition according to any one of ⁇ 1> to ⁇ 20>.
  • a laminate comprising:
  • a manufacturing method for a cured substance further comprising:
  • a manufacturing method for a laminate comprising:
  • a manufacturing method for a semiconductor device comprising:
  • a semiconductor device comprising:
  • a photosensitive resin composition having excellent resolution in a case of forming a pattern of a cured substance, a cured substance obtained by curing the composition, a laminate including the cured substance, a manufacturing method for a cured substance, a manufacturing method for a laminate, a manufacturing method for a semiconductor device including a manufacturing method for a cured substance, and a semiconductor device including a cured substance.
  • FIG. 1 is a schematic cross-sectional view of a state where a cured substance is formed on a silicon wafer on which a copper wire is formed.
  • a numerical value range described by using “to” means a range including numerical values described before and after the preposition “to” as a lower limit value and an upper limit value, respectively.
  • step means not only an independent step but also a step that cannot be clearly distinguished from other steps as long as the desired action of the step can be achieved.
  • the description means the group includes a group (an atomic group) having a substituent as well as a group (an atomic group) having no substituent.
  • the “alkyl group” includes not only an alkyl group that does not have a substituent (an unsubstituted alkyl group) but also an alkyl group that has a substituent (a substituted alkyl group).
  • the “exposure” includes not only exposure using light but also exposure using corpuscular beams such as an electron beam and an ion beam, unless otherwise specified.
  • examples of the light that is used for exposure include an actinic ray such as a bright line spectrum of a mercury lamp, a far ultraviolet ray represented by an excimer laser, an extreme ultraviolet ray (EUV light), an X-ray, or an electron beam, and a radioactive ray.
  • (meth)acrylate means one or both of “acrylate” and “methacrylate”
  • (meth)acryl means one or both of “acryl” and “methacryl”
  • (meth)acryloyl means one or both of “acryloyl” and “methacryloyl”.
  • Me represents a methyl group
  • Et represents an ethyl group
  • Bu represents a butyl group
  • Ph represents a phenyl group
  • the total solid content refers to the total mass of components excluding a solvent from the entire components of the composition.
  • the concentration of solid contents is a mass percentage of other components excluding a solvent with respect to the total mass of the composition.
  • weight-average molecular weight (Mw) and number-average molecular weight (Mn) are each a value measured using gel permeation chromatography (GPC) unless otherwise specified, which are defined as a polystyrene equivalent value.
  • the weight-average molecular weight (Mw) and the number-average molecular weight (Mn) can be determined, for example, by using HLC-8220 GPC (manufactured by Tosoh Corporation) and using GUARD COLUMN HZ-L, TSKgel Super HZM-M, TSK gel Super HZ4000, TSK gel Super HZ3000, and TSK gel Super HZ2000 (all of which are manufactured by Tosoh Corporation) as a column connected in series.
  • the measurements of the above molecular weights are carried out using tetrahydrofuran (THF) as an eluent unless otherwise specified.
  • THF tetrahydrofuran
  • NMP N-methyl-2-pyrrolidone
  • THF is not suitable as the eluent
  • solubility is low.
  • the detection in GPC measurement is carried out using a detector with an ultraviolet ray (a UV ray) of a wavelength of 254 nm unless otherwise specified.
  • a composition may contain, as each component contained in the composition, two or more compounds corresponding to the component unless otherwise specified.
  • the content of each component in the composition means the total content of all the compounds corresponding to the component unless otherwise specified.
  • a photosensitive resin composition according to a first aspect of the present invention includes a resin having a repeating unit represented by Formula (1-1) and a photosensitizing agent.
  • a photosensitive resin composition according to a second aspect of the present invention is a photosensitive resin composition including at least one resin selected from the group consisting of a polyimide and a precursor of the polyimide, and a photosensitizing agent, in which the photosensitive resin composition is applied to a silicon wafer on which a copper wire having a height of 15 ⁇ m, a width of 20 ⁇ m, and a taper angle of 85 degrees is formed in a 1:1 line-and-space pattern, with a film thickness such that a distance from a base material to a film surface is 20 ⁇ m, and a maximum value of a difference in the distance from the base material to the film surface of a cured substance obtained by heating at 230° C.
  • the photosensitive resin composition is applied to the silicon wafer to form a film having a thickness of 15 ⁇ m, and a change rate in thickness of the cured substance obtained by heating at 230° C. for 3 hours after entire surface exposure with respect to a thickness of 15 ⁇ m of the cured substance before exposure is less than 15%.
  • first resin composition and the second resin composition are simply referred to as a “resin composition”.
  • the resin having a repeating unit represented by Formula (1-1), which is contained in the first resin composition is also referred to as a “first specific resin”.
  • first specific resin the resin having a repeating unit represented by Formula (1-1), which is contained in the first resin composition
  • second specific resin at least one resin selected from the group consisting of a polyimide and a precursor of the polyimide, which is contained in the second resin composition, is also referred to as a “second specific resin”.
  • the resin composition according to the embodiment of the present invention is preferably used for forming a photosensitive film that is subjected to exposure and development, and more preferably used for forming a film that is subjected to exposure and development using a developer containing an organic solvent.
  • the resin composition according to the embodiment of the present invention can be used, for example, for forming an insulating film of a semiconductor device, an interlayer insulating film for a re-distribution layer, a stress buffer film, or the like, and it is preferably used for forming an interlayer insulating film for an insulating member.
  • the insulating member is a member formed for the purpose of insulating members intended for conduction, such as wiring lines.
  • the volume resistivity of the insulating member is preferably 1 ⁇ 10 8 ⁇ cm or more, more preferably 1 ⁇ 10 10 ⁇ cm or more, and still more preferably 1 ⁇ 10 12 ⁇ cm or more.
  • one of the preferred aspects of the present invention is that the resin composition according to the embodiment of the present invention is used for forming an interlayer insulating film for a re-distribution layer.
  • the resin composition according to the embodiment of the present invention is preferably used for forming a photosensitive film that is subjected to negative-tone development.
  • the negative-tone development refers to development in which, in exposure and development, a non-exposed portion is removed by the development
  • the positive-tone development means a development in which an exposed portion is removed by the development
  • the exposure method for example, the following ones in the description of the manufacturing method for a cured substance, which will be described later, are used: an exposure method to be described in the exposure step, and a developer and a development method to be described in the development step.
  • the resin composition according to the embodiment of the present invention has excellent resolution in a case of forming a pattern of a cured substance.
  • the photosensitive resin composition according to the first aspect of the present invention includes a resin having a repeating unit represented by Formula (1-1) and a photosensitizing agent.
  • a photosensitive resin composition according to a second aspect of the present invention is a photosensitive resin composition including at least one resin selected from the group consisting of a polyimide and a precursor of the polyimide, and a photosensitizing agent, in which the photosensitive resin composition is applied to a silicon wafer on which a copper wire having a height of 15 ⁇ m, a width of 20 ⁇ m, and a taper angle of 85 degrees is formed in a 1:1 line-and-space pattern, with a film thickness such that a distance from a base material to a film surface is 20 ⁇ m, and a maximum value of a difference in the distance from the base material to the film surface of a cured substance obtained by heating at 230° C.
  • the photosensitive resin composition is applied to the silicon wafer to form a film having a thickness of 15 am, and a change rate in thickness of the cured substance obtained by heating at 230° C. for 3 hours after entire surface exposure with respect to a thickness of 15 ⁇ m of the cured substance before exposure (hereinafter, also referred to as “shrinkage ratio”) is less than 15%.
  • the photosensitive resin composition as described above has excellent resolution of a pattern obtained by exposure and development.
  • the photosensitive resin composition according to the first aspect of the present invention it is considered that the amount of decomposition products decomposed from the resin by exposure, development, and heating is small, and the resin itself has a relatively rigid structure, and thus both the roughness and the shrinkage ratio after curing are small.
  • both the roughness and the shrinkage ratio after curing are small.
  • the composition can be applied in a thin manner even in consideration of the thickness of the pattern formed after curing, and thus the resolution is excellent.
  • JP2020-255859A and JP2021/039782A do not disclose a resin composition corresponding to the resin composition according to the embodiment of the present invention.
  • the flatness of the first resin composition according to the embodiment of the present invention is preferably less than 30%, more preferably less than 20%, and still more preferably less than 15%.
  • the flatness of the second resin composition according to the embodiment of the present invention is less than 30%, preferably less than 20%, and more preferably less than 15%.
  • the flatness is calculated as the maximum value of the difference in the distance from the base material to the film surface of a cured substance obtained by applying a resin composition to a silicon wafer on which a copper wire having 1:1 line-and-space pattern with a height of 15 ⁇ m and a width of 20 ⁇ m and a taper angle of 85 degrees is formed and heating the silicon wafer at 230° C. for 3 hours, where the film thickness is such that the distance from the base material to the film surface is 20 ⁇ m.
  • the distance from the base material of the cured substance to the film surface is measured as a film thickness of a film consisting of the resin composition in the space portion of the copper wire.
  • the method of applying the resin composition is not particularly limited, and any method may be used as long as the distance from the base material to the film surface is 20 ⁇ m.
  • a spin coating method can be used.
  • the spin coating method may be performed a plurality of times.
  • an application method may be appropriately selected from known methods such as a dip coating method, an air knife coating method, a curtain coating method, a wire bar coating method, a gravure coating method, an extrusion coating method, a spray coating method, a slit coating method, and an ink jet method.
  • the resin composition contains a solvent
  • the distance from the base material to the film surface after drying is 20 ⁇ m.
  • drying is carried out until the amount of the solvent in the film is 0.5% by mass or less.
  • the drying conditions are not particularly limited, but can be carried out by drying with heating.
  • the pressure may be further reduced.
  • the drying can be carried out in the atmosphere.
  • the treatment can also be carried out under an inert gas replacement such as nitrogen, under vacuum, or the like.
  • the drying means is not particularly limited, and examples thereof include a hot plate. However, in a case where the above-described pressure reduction, inert gas replacement, and the like are required, an oven with a pressure reduction function, an oven with a gas replacement function, or the like can also be used.
  • the heating temperature (drying temperature) can be set to, for example, 100° C.
  • the drying temperature may be appropriately changed to 70° C. to 130° C., preferably 90° C. to 120° C., depending on the kind or the like of the solvent contained in the resin composition.
  • the drying time (the time during which the heating is performed at the above-described heating temperature) can be, for example, 5 minutes. However, in a case where it is difficult to carry out drying for 5 minutes, the drying time may be appropriately changed to 30 seconds to 20 minutes, and preferably 1 minute to 10 minutes, depending on the kind or the like of the solvent contained in the resin composition.
  • the temperature rising rate during heating is not particularly limited, and for example, it can be set to 5° C./min. In a case where the drying at the above-described temperature rising rate is difficult, the temperature rising rate may be appropriately changed to 1 to 12° C./min or 2 to 10° C./min depending on the kind or the like of the solvent contained in the resin composition.
  • the film of the resin composition obtained by the above-described application is heated at 230° C. for 3 hours to obtain a cured substance.
  • the film of the resin composition obtained by the application is subjected to heating while being exposed as little as possible. In addition, contact with a solvent such as a developer can also be avoided as much as possible.
  • the heating can be carried out in an oven under a nitrogen atmosphere.
  • the pressure in the heating is set to 1 atm (101,325 Pa).
  • the temperature rising rate in the heating can be, for example, 10° C./min.
  • the temperature rising rate may be appropriately changed to 1 to 12° C./min or 2 to 10° C./min depending on the kind or the like of the solvent contained in the resin composition.
  • the heating time (time exposed to 230° C.) in the above-described heating is set to 3 hours.
  • the film thickness of the cured substance is measured after cooling the cured substance to 25° C.
  • the flatness can be measured by a method described in Examples described later.
  • the dissolution rate of the cured substance can be adjusted by the structure, the content, and the like of the specific resin, the polymerizable compound, and the like contained in the resin composition.
  • the shrinkage ratio of the first resin composition according to the embodiment of the present invention is preferably less than 15%, more preferably less than 12%, and still more preferably less than 10%.
  • the shrinkage ratio of the second resin composition according to the embodiment of the present invention is less than 15%, preferably less than 12%, and more preferably less than 10%.
  • the shrinkage ratio is calculated as a change rate in thickness of a cured substance obtained by applying the resin composition to a silicon wafer to form a film having a film thickness of 15 ⁇ m, exposing the film over the entire surface, and heating the film at 230° C. for 3 hours, with respect to a thickness of 15 ⁇ m before the exposure.
  • the shrinkage ratio is calculated by the following calculation formula in a case where the film thickness of the cured substance is denoted by film thickness B.
  • Examples of the method of applying the resin composition to the silicon wafer include the application methods described in the above description of the flatness, except that the thickness is set to 15 ⁇ m.
  • the resin composition contains a solvent
  • the distance from the base material to the film surface after drying is 15 ⁇ m.
  • Examples of the method of performing the above-described drying include the drying method described in the above-described description of the flatness, except that the thickness is set to 15 ⁇ m.
  • the entire surface exposure is performed by a method of exposing the entire surface with i-rays at an exposure energy of 500 mJ/cm 2 using a stepper (for example, Nikon NSR 2005 i9C).
  • a stepper for example, Nikon NSR 2005 i9C.
  • the exposure wavelength and the exposure sensitivity can be appropriately changed.
  • the exposure wavelength and the exposure sensitivity are changed. Whether or not the photosensitizing agent responds to exposure can be determined by a change in the structure of the photosensitizing agent.
  • the film of the resin composition after the entire surface exposure is heated at 230° C. for 3 hours to obtain a cured substance.
  • Examples of the method of performing the above-described heating include the heating method described in the above-described description of the flatness.
  • the above-described shrinkage ratio can be adjusted by the structure, the content, and the like of the specific resin, the polymerizable compound, and the like contained in the resin composition.
  • the film thickness of the cured substance is measured after cooling the cured substance to 25° C.
  • the film in a case where the resin composition is applied onto a silicon wafer satisfies the following condition (1).
  • Condition (1) the dissolution rate of the film in cyclopentanone is 0.1 ⁇ m/sec or more and less than 0.6 ⁇ m/sec.
  • the lower limit of the dissolution rate of the film is preferably 0.05 ⁇ m/sec or more and more preferably 0.10 to 0.2 ⁇ m/sec or more.
  • the upper limit of the dissolution rate of the film is preferably 1.2 ⁇ m/sec or less and more preferably 0.6 to 1.0 ⁇ m/sec or less.
  • Examples of the method of applying the resin composition to the silicon wafer include the application methods described in the description of the flatness above.
  • the resin composition contains a solvent, it is preferable to carry out drying after the above-described application.
  • Examples of the method of performing the above-described drying include the drying methods described in the above-described description of the flatness.
  • the dissolution rate of the film in cyclopentanone can be calculated by immersing a silicon wafer on which the film is formed in cyclopentanone for 30 seconds and measuring the film thickness of the film before and after immersion with an ellipsometer.
  • the film is immersed in cyclopentanone in a state in which the film is not subjected to heating other than the drying.
  • the amount of cyclopentanone used for the immersion is preferably 1000 times the volume of the film.
  • the temperatures of the cyclopentanone, the film, and the silicon wafer during the immersion are set to 23° C.
  • the immersion time may be appropriately changed to calculate the dissolution rate.
  • the dissolution rate of the film can be adjusted by the structure, the content, and the like of the specific resin, the polymerizable compound, and the like contained in the resin composition.
  • a cured substance obtained by heating the resin composition at 230° C. for 3 hours satisfies the following condition (2).
  • Condition (2) a change rate in film thickness before and after immersion is less than 20% after the cured substance is immersed at 75° C. for 15 minutes in a mixture of dimethyl sulfoxide and a 25% by mass aqueous tetramethylammonium hydroxide solution in 90:10 (mass ratio).
  • the above-described change rate in film thickness is preferably less than 15% and more preferably less than 10%.
  • the change rate in film thickness in the condition (2) can be calculated as 100 ⁇ (film thickness after immersion/film thickness before immersion ⁇ 100) (%).
  • the cured substance is obtained by applying the resin composition onto a silicon wafer to form a film and then heating the film at 230° C. for 3 hours.
  • Examples of the method of applying the resin composition to the silicon wafer include the application methods described in the description of the flatness above.
  • the resin composition contains a solvent, it is preferable to carry out drying after the above-described application.
  • Examples of the method of performing the above-described drying include the drying methods described in the above-described description of the flatness.
  • the film thickness of the film formed by the application is not particularly limited, but can be, for example, 15 ⁇ m.
  • the film formed by the above-described application (in a case of performing drying, the film after drying) is heated at 230° C. for 3 hours to obtain a cured substance.
  • Examples of the method of performing the above-described heating include the heating method described in the above-described description of the flatness.
  • the change rate in film thickness can be measured by a method described in Examples described later.
  • the above-described change rate in film thickness can be adjusted by the structure, the content, and the like of the specific resin, the polymerizable compound, and the like contained in the resin composition.
  • a cured substance obtained by heating the resin composition at 230° C. for 3 hours satisfies the following condition (3).
  • a coefficient of thermal expansion of the cured substance in a temperature range of 25° C. to 125° C. is more than 20 ppm/° C. and 75 ppm/° C. or less.
  • the coefficient of thermal expansion is preferably 60 ppm/° C. or less and more preferably 50 ppm/° C. or less.
  • the cured substance is obtained by the same method as the method described in the above-described description of the chemical resistance.
  • the coefficient of thermal expansion is calculated as a value obtained by subjecting the cured substance to the temperature rising and falling conditions shown in the following (1) to (4) and dividing the elongation (displacement) of the sample at 25° C. and 125° C. in the process (3) by the temperature difference.
  • the temperature is raised from room temperature to 130° C. at a temperature rising rate of 5° C./min.
  • the temperature is raised from 10° C. to 220° C. at a temperature rising rate of 5° C./min.
  • the elongation (displacement) of the specimen was measured, and a calculation was carried out to determine a value obtained by dividing the elongation (displacement) of the specimen at 25° C. and 125° C. in the process (3) by the temperature difference (100° C.), where the value was defined as the coefficient of thermal expansion.
  • the coefficient of thermal expansion of the film can be measured by a method described in Examples described later.
  • the coefficient of thermal expansion can be adjusted by the structure, the content, and the like of the specific resin, the polymerizable compound, and the like contained in the resin composition.
  • the pH of the resin composition is preferably 3.0 to 11.0, more preferably 4.0 to 9.0, and still more preferably 4.0 to 8.0.
  • the pH can be measured using a pH meter.
  • HM-42 (manufactured by DKK-TOA CORPORATION) is used as a pH meter
  • GST-58415 (manufactured by DKK-TOA CORPORATION) is used as an electrode
  • a 3.3 mol/L potassium chloride aqueous solution (manufactured by FUJIFILM Wako Pure Chemical Corporation) is used as an internal liquid of the electrode, and the measurement can be performed by bringing the electrode into direct contact with the resin composition.
  • the second specific resin is preferably at least one resin selected from the group consisting of polyimide and a precursor of the polyimide, and more preferably polyimide.
  • the polyimide precursor refers to a resin which is polyimide due to a change in molecular structure caused by an external stimulus, and a resin which is polyimide due to a change in molecular structure caused by heat is preferable, and a resin which is polyimide due to a ring closure reaction caused by heat to form a ring structure is more preferable.
  • the polyimide is preferably at least one resin selected from the group consisting of polyimide, polyamideimide, and polyesterimide.
  • the polyimide is preferably at least one resin selected from the group consisting of a polyimide having a repeating unit represented by Formula (1-1) which will be described later, a polyimide (polyamideimide) having a repeating unit represented by Formula (1-3) which will be described later, and a polyimide (polyesterimide) having a repeating unit represented by Formula (1-5) which will be described later.
  • the second specific resin preferably has a polymerizable group.
  • the polymerizable group may be a cationically polymerizable group, but is preferably a radically polymerizable group.
  • Examples of the polymerizable group include an epoxy group, an oxetanyl group, an alkoxymethyl group, an acyloxymethyl group, a methylol group, a blocked isocyanate group, and a group containing an ethylenically unsaturated bond, but a group containing an ethylenically unsaturated bond is preferable.
  • the group having an ethylenically unsaturated bond is preferably a radically polymerizable group.
  • examples of the group containing an ethylenically unsaturated bond include a vinyl group, a vinyl ether group, an allyl group, an isoallyl group, a 2-methylallyl group, a (meth)acrylamide group, and a (meth)acryloyloxy group, and from the viewpoint of reducing the polarity and reducing the dielectric constant of the obtained cured substance, a vinyl group or a vinyl ether group is preferable.
  • the vinyl group is preferably directly bonded to an aromatic ring structure.
  • the direct bonding of a certain structure A and another structure B means that the structure A and the structure B are directly bonded by a single bond without a linking group being interposed therebetween.
  • the second specific resin is preferably a resin having a ring structure with 5 or more ring members in a side chain.
  • a main chain of the resin indicates the relatively longest bonding chain in the resin molecule.
  • an atom included as a ring member in the ring structure is an atom included in the main chain.
  • the side chain of the resin refers to a molecular chain bonded to the main chain, and the molecular chain may or may not have a repeating unit. That is, the molecular chain may or may not include a repeating structure.
  • the molecular chain is preferably a molecular chain composed of 6 or more atoms, more preferably a molecular chain composed of 10 or more atoms, and still more preferably a molecular chain composed of 15 or more atoms.
  • An upper limit of the number of atoms included in the molecular chain is not particularly limited, but is, for example, preferably 1,000 or less and more preferably 500 or less.
  • the side chain in the second specific resin is preferably bonded to a carbon atom included in the main chain, and in a case where the side chain is represented by R, the side chain R is preferably bonded to a carbon atom C of the main chain as C-R. That is, it is preferable that there is only one bond to the main chain in one side chain.
  • the ring structure with 5 or more ring members is preferably a ring structure with 5 to 20 ring members, and more preferably a ring structure with 5 to 12 ring members.
  • the ring structure with 5 or more ring members may be any of an aromatic ring or an aliphatic ring, and is preferably an aromatic ring or an aliphatic hydrocarbon ring and more preferably an aromatic ring.
  • the aromatic ring may be any of an aromatic hydrocarbon ring or a heteroaromatic ring, but is preferably an aromatic hydrocarbon ring or a heteroaromatic ring containing a nitrogen atom as a ring member.
  • the aromatic hydrocarbon ring is preferably an aromatic hydrocarbon ring having 6 to 20 carbon atoms, more preferably an aromatic hydrocarbon ring having 6 to 10 carbon atoms, and still more preferably a benzene ring.
  • heteroaromatic ring examples include a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring, an imidazole ring, a triazole ring, a tetrazole ring, an oxazole ring, a pyridine ring, a pyridazine ring, a pyrazine ring, a triazine ring, an indole ring, an indazole ring, a benzimidazole ring, and a purine ring.
  • aliphatic ring examples include an aliphatic hydrocarbon ring having 5 to 20 carbon atoms, a pyrrolidine ring, a pyrroline ring, a pyrazolidine ring, an imidazolidine ring, a tetrahydrofuran ring, a tetrahydrothiophene ring, a piperidine ring, a piperazine ring, a tetrahydropyran ring, a dioxane ring, and a morpholine ring.
  • a benzene ring, a cyclohexane ring, or an adamantane ring is preferable, and a benzene ring is more preferable.
  • a hydrogen atom that is bonded to the ring member by a single bond without a linking group being interposed therebetween may be substituted.
  • the substituent include an alkyl group, an aryl group, a halogen atom, and a polymerizable group described later.
  • the content of the ring structure with 5 or more ring members in the second specific resin is preferably 0.01 to 5.0 mmol/g, more preferably 0.1 to 4.0 mmol/g, and still more preferably 0.5 to 2.5 mmol/g with respect to 1 g of the specific resin.
  • the second specific resin preferably has a structure represented by Formula (A-1).
  • L A1 represents a single bond or an (m+1)-valent linking group
  • Cy's each independently represent a ring structure with 5 or more ring members, which may have a substituent
  • m represents an integer of 1 or more
  • * represents a bonding site to another structure.
  • L A1 is preferably an (m+1)-valent linking group.
  • a preferred aspect of L A1 is the same as a preferred aspect of L 1 in Formula (R-1) described later.
  • a preferred aspect of Cy is the same as the preferred aspect of the ring structure with 5 or more ring members described above.
  • Cy is directly bonded to a polymerizable group described later.
  • * represents a bonding site to another structure, and it preferably represents a bonding site to an atom included in the main chain of the resin, and more preferably represents a bonding site to a carbon atom included in the main chain.
  • the carbon atom is preferably a tertiary carbon atom or a quaternary carbon atom.
  • the content of the structure represented by Formula (A-1) in the second specific resin is preferably 0.01 to 5.0 mmol/g, more preferably 0.1 to 4.0 mmol/g, and still more preferably 0.5 to 2.5 mmol/g with respect to 1 g of the specific resin.
  • the first specific resin has a repeating unit represented by Formula (1-1).
  • the second specific resin preferably has a repeating unit represented by Formula
  • X 1 represents an organic group including a structure obtained by removing two or more hydrogen atoms from a structure represented by any of Formula (V-1) to Formula (V-10)
  • Y 1 represents an organic group including a structure obtained by removing two or more hydrogen atoms from a structure represented by any of Formula (V-1) to Formula (V-6) and Formula (V-8)
  • R 1 's each independently represent an organic group having a polymerizable group
  • m represents an integer of 0 to 4
  • n represents an integer of 1 or more.
  • R 1 's each independently represent an organic group having a polymerizable group.
  • the preferred aspect of the polymerizable group is the same as the preferred aspect of the polymerizable group described above regarding the second specific resin.
  • R 1 includes the above-described ring structure with 5 or more ring members.
  • R 1 is preferably a structure represented by Formula (R-1).
  • L 1 represents an (a2+1)-valent linking group
  • Z 1 represents an aromatic group or a cyclic aliphatic group
  • a 1 represents a polymerizable group
  • a1 represents an integer of 0 or more and equal to or less than a maximum number of substituents of Z 1
  • a2 represents an integer of 1 or more
  • * represents a bonding site to X 1 or Y 1 in Formula (1-1).
  • L 1 is preferably a group represented by Formula (L-1).
  • L x represents an (a2+1)-valent linking group
  • a2 represents an integer of 1 or more
  • * represents a bonding site to X 1 or Y 1 in Formula (1-1)
  • # represents a bonding site to Z 1 in Formula (R-1).
  • L x is preferably an alkylene group, more preferably an alkylene group having 1 to 10 carbon atoms, still more preferably an alkylene group having 1 to 4 carbon atoms, and particularly preferably a methylene group.
  • the preferred aspect of a2 in Formula (L-1) is the same as the preferred aspect of a2 in Formula (R-1).
  • Z 1 in Formula (R-1) represents an aromatic group or a cyclic aliphatic group.
  • the preferred aspect of these groups is the same as a preferred aspect of the ring structure with 5 or more ring members in the above-described first specific resin.
  • a 1 in Formula (R-1) represents a polymerizable group, and the preferred aspect of the polymerizable group is the same as the preferred aspect of the polymerizable group in the first specific resin and the second specific resin described above.
  • At least one of A 1 's in Formula (R-1) included in Formula (1-1) is preferably a vinyl group, a (meth)acryloxy group, a vinyl ether group, an allyl group, an epoxy group, or a group including these groups, and more preferably a vinyl group or a vinyl ether group.
  • a1 is preferably an integer of 0 to 2, and more preferably 0 or 1.
  • an aspect in which a1 is 1 or 2 is also one of the preferred aspects of the present invention.
  • a2 represents an integer of 1 or more, and is preferably 1 or 2 and more preferably 1.
  • the number of ester bonds included in Formula (R-1) is preferably 1 or 0.
  • X 1 represents an organic group including a structure obtained by removing two or more hydrogen atoms from a structure represented by any of Formulae (V-1) to (V-10).
  • the resolution is improved by being an organic group including a structure obtained by removing two or more hydrogen atoms from a structure represented by any one of Formulae (V-1) to Formula (V-10).
  • the organic group is an organic group including a structure obtained by removing two or more hydrogen atoms from a structure represented by any of Formula (V-1) to Formula (V-5), and thus, effects such as suppression of generation of development residues, reduction of the dielectric constant of the cured substance, and reduction of the coefficient of thermal expansion can also be obtained.
  • the organic group is an organic group including a structure obtained by removing two or more hydrogen atoms from a structure represented by any of Formula (V-6) to Formula (V-10), effects such as that the pattern is less likely to be tapered due to improvement in the transmittance of ultraviolet light and that the tolerance to the exposure amount is wide can also be obtained.
  • R X1 's each independently represent a hydrogen atom, an alkyl group, or a halogenated alkyl group.
  • R X2 and R X3 each independently represent a hydrogen atom or a substituent, and R X2 and R X3 may be bonded to each other to form a ring structure.
  • R X5 's each independently represent a hydrogen atom, an alkyl group, or a halogenated alkyl group.
  • R X1 's are each independently preferably an alkyl group or a halogenated alkyl group, more preferably an alkyl group having 1 to 4 carbon atoms or a halogenated alkyl group having 1 to 4 carbon atoms, and still more preferably a methyl group or a trifluoromethyl group.
  • the halogenated alkyl group refers to a group in which at least one hydrogen atom of an alkyl group is substituted with a halogen atom. As the halogen atom, F or Cl is preferable, and F is more preferable.
  • R X2 and R X3 are each independently preferably a hydrogen atom.
  • R X2 and R X3 are bonded to each other to form a ring structure
  • the structure formed by the bonding of R X2 and R X3 is preferably a single bond, —O—, or —CR 2 —, more preferably —O— or —C(R) 2 —, and still more preferably —O—.
  • R represents a hydrogen atom or a monovalent organic group, preferably a hydrogen atom, an alkyl group, or an aryl group, and more preferably a hydrogen atom.
  • R X5 's are each independently preferably an alkyl group or a halogenated alkyl group, more preferably an alkyl group having 1 to 4 carbon atoms or a halogenated alkyl group having 1 to 4 carbon atoms, and still more preferably a methyl group or a trifluoromethyl group.
  • the halogenated alkyl group refers to a group in which at least one hydrogen atom of an alkyl group is substituted with a halogen atom. As the halogen atom, F or Cl is preferable, and F is more preferable.
  • X 1 is a group including a structure obtained by removing two or more hydrogen atoms from a structure represented by Formula (V-1)
  • X 1 is preferably a group represented by Formula (V-1-1).
  • * represents a bonding site to four carbonyl groups to which X 1 in Formula (1-1) is bonded
  • n1 represents an integer of 0 to 5
  • n1 is an integer of 1 to 5.
  • the hydrogen atom in the following structure may be further substituted with a known substituent such as a hydroxy group or a hydrocarbon group.
  • m in Formula (1-1) is an integer of 1 to 4
  • m hydrogen atoms are substituted with R 1 in Formula (1-1).
  • X 1 is a group including a structure obtained by removing two or more hydrogen atoms from a structure represented by Formula (V-2)
  • X 1 is preferably a group represented by Formula (V-2-1) or Formula (V-2-2)
  • X 1 is preferably a group represented by Formula (V-2-2).
  • a bond that intersects with a side of a ring structure means that any hydrogen atom in the ring structure is substituted.
  • L X1 represents a single bond or —O—
  • * represents a bonding site to four carbonyl groups to which X 1 in Formula (1-1) is bonded.
  • R X1 the definition and preferred aspect of R X1 are as described above.
  • the hydrogen atom in these structures may be further substituted with a known substituent such as a hydroxy group or a hydrocarbon group.
  • m in Formula (1-1) is an integer of 1 to 4, it is preferable that m hydrogen atoms are substituted with R 1 in Formula (1-1).
  • X 1 is a group including a structure obtained by removing two or more hydrogen atoms from a structure represented by Formula (V-5)
  • X 1 is preferably a group represented by Formula (V-5-1).
  • * represents a bonding site to four carbonyl groups to which X 1 in Formula (1-1) is bonded.
  • the hydrogen atom in the following structure may be further substituted with a known substituent such as a hydroxy group or a hydrocarbon group.
  • m in Formula (1-1) is an integer of 1 to 4, it is preferable that m hydrogen atoms are substituted with R 1 in Formula (1-1).
  • X 1 is a group including a structure obtained by removing two or more hydrogen atoms from a structure represented by Formula (V-6)
  • X 1 is preferably a group represented by Formula (V-6-1).
  • * represents a bonding site to four carbonyl groups to which X 1 in Formula (1-1) is bonded.
  • the hydrogen atom in the following structure may be further substituted with a known substituent such as a hydroxy group or a hydrocarbon group.
  • m in Formula (1-1) is an integer of 1 to 4, it is preferable that m hydrogen atoms are substituted with R 1 in Formula (1-1).
  • X 1 is a group including a structure obtained by removing two or more hydrogen atoms from a structure represented by Formula (V-7)
  • X 1 is preferably a group represented by Formula (V-7-1).
  • * represents a bonding site to four carbonyl groups to which X 1 in Formula (1-1) is bonded.
  • the hydrogen atom in the following structure may be further substituted with a known substituent such as a hydroxy group or a hydrocarbon group.
  • m in Formula (1-1) is an integer of 1 to 4, it is preferable that m hydrogen atoms are substituted with R 1 in Formula (1-1).
  • X 1 is a group including a structure obtained by removing two or more hydrogen atoms from a structure represented by Formula (V-8)
  • X 1 is preferably a group represented by Formula (V-8-1).
  • * represents a bonding site to four carbonyl groups to which X 1 in Formula (1-1) is bonded.
  • the hydrogen atom in the following structure may be further substituted with a known substituent such as a hydroxy group or a hydrocarbon group.
  • m in Formula (1-1) is an integer of 1 to 4, it is preferable that m hydrogen atoms are substituted with R 1 in Formula (1-1).
  • X 1 is a group including a structure obtained by removing two or more hydrogen atoms from a structure represented by Formula (V-9)
  • X 1 is preferably a group represented by Formula (V-9-1).
  • * represents a bonding site to four carbonyl groups to which X 1 in Formula (1-1) is bonded.
  • the hydrogen atom in the following structure may be further substituted with a known substituent such as a hydroxy group or a hydrocarbon group.
  • m in Formula (1-1) is an integer of 1 to 4, it is preferable that m hydrogen atoms are substituted with R 1 in Formula (1-1).
  • X 1 is a group including a structure obtained by removing two or more hydrogen atoms from a structure represented by Formula (V-10)
  • X 1 is preferably a group represented by Formula (V-10-1).
  • * represents a bonding site to four carbonyl groups to which X 1 in Formula (1-1) is bonded.
  • the hydrogen atom in the following structure may be further substituted with a known substituent such as a hydroxy group or a hydrocarbon group.
  • m in Formula (1-1) is an integer of 1 to 4, it is preferable that m hydrogen atoms are substituted with R 1 in Formula (1-1).
  • X 1 may be a group obtained by removing m hydrogen atoms from a group represented by R 132 in Formula (4) described later.
  • X 1 does not contain an imide structure in the structure.
  • X 1 does not contain a urethane bond, a urea bond, and an amide bond in the structure.
  • the urethane bond is a bond represented by *—O—C( ⁇ O)—NR N —*, where R N represents a hydrogen atom or a monovalent organic group, and *'s each represent a bonding site to a carbon atom.
  • R N is preferably a hydrogen atom, an alkyl group, or an aryl group, and more preferably a hydrogen atom.
  • the urea bond is a bond represented by *—NR N —C( ⁇ O)—NR N *, where R N 's each independently represent a hydrogen atom or a monovalent organic group, and *'s each represent a bonding site to a carbon atom.
  • R N is a bond represented by *—NR N —C( ⁇ O)—NR N *, where R N 's each independently represent a hydrogen atom or a monovalent organic group, and *'s each represent a bonding site to a carbon atom.
  • R N is as described above.
  • R N represents a hydrogen atom or a monovalent organic group
  • *'s each represent a bonding site to a carbon atom.
  • the preferred aspect of R N is as described above.
  • X 1 does not contain an ester bond in the structure.
  • ester bond is a bond represented by *—O—C( ⁇ O)—*.
  • X 1 does not contain an imide structure, a urethane bond, a urea bond, and an amide bond, and it is preferable that X 1 does not contain an imide structure, a urethane bond, a urea bond, an amide bond, and an ester bond.
  • Y 1 is preferably a group including a structure obtained by removing two or more hydrogen atoms from the structures represented by any of Formulae (V-1) to (V-6) and (V-8) described above.
  • the resolution is improved by being an organic group including a structure obtained by removing two or more hydrogen atoms from a structure represented by any one of Formulae (V-1) to Formula (V-6), or Formula (V-8).
  • the organic group is an organic group including a structure obtained by removing two or more hydrogen atoms from a structure represented by any of Formula (V-1) to Formula (V-5), and thus, effects such as suppression of generation of development residues, reduction of the dielectric constant of the cured substance, and reduction of the coefficient of thermal expansion can also be obtained.
  • the organic group is an organic group including a structure obtained by removing two or more hydrogen atoms from a structure represented by any of Formula (V-6) to Formula (V-8), effects such as that the pattern is less likely to be tapered due to improvement in the transmittance of ultraviolet light and that the tolerance to the exposure amount is wide can also be obtained.
  • Y 1 is a group including a structure obtained by removing two or more hydrogen atoms from a structure represented by Formula (V-1)
  • Y 1 is preferably a group obtained by removing n hydrogen atoms from a group represented by Formula (V-1-2).
  • * represents a bonding site to two nitrogen atoms to which Y 1 in Formula (1-1) is bonded
  • n1 represents an integer of 1 to 5.
  • n hydrogen atoms in the following structure are substituted with R 1 in Formula (1-1).
  • n has the same meaning as n in Formula (1-1).
  • the hydrogen atom in the following structure may be further substituted with a known substituent such as a hydroxy group or a hydrocarbon group.
  • Y 1 is a group including a structure obtained by removing two or more hydrogen atoms from a structure represented by Formula (V-2), Y 1 is preferably a group represented by Formula (V-2-3) or Formula (V-2-4), and from the viewpoint of reducing the dielectric constant of the cured substance or the like, Y 1 is preferably a group represented by Formula (V-2-4).
  • L X1 represents a single bond or —O—
  • * represents a bonding site to two nitrogen atoms to which Y 1 in Formula (1-1) is bonded.
  • R X1 is as described above.
  • n hydrogen atoms in the following structure are substituted with R 1 in Formula (1-1). n has the same meaning as n in Formula (1-1).
  • the hydrogen atom in these structures may be further substituted with a known substituent such as a hydroxy group or a hydrocarbon group.
  • Y 1 is a group including a structure obtained by removing two or more hydrogen atoms from a structure represented by Formula (V-3), Y 1 is preferably a group represented by Formula (V-3-3) or Formula (V-3-4), and from the viewpoint of reducing the dielectric constant of the cured substance or the like, Y 1 is preferably a group represented by Formula (V-3-3).
  • * represents a bonding site to two nitrogen atoms to which Y 1 in Formula (1-1) is bonded.
  • R X2 and R X3 are as described above.
  • n hydrogen atoms in the following structure are substituted with R 1 in Formula (1-1).
  • n has the same meaning as n in Formula (1-1).
  • the hydrogen atom in these structures may be further substituted with a known substituent such as a hydroxy group or a hydrocarbon group.
  • Y 1 is a group including a structure obtained by removing two or more hydrogen atoms from a structure represented by Formula (V-4), Y 1 is preferably a group represented by Formula (V-4-2).
  • * represents a bonding site to two nitrogen atoms to which Y 1 in Formula (1-1) is bonded
  • n1 represents an integer of 0 to 5.
  • an aspect in which n1 is 0 is also one of the preferred aspects of the present invention.
  • n hydrogen atoms in the following structure are substituted with R 1 in Formula (1-1).
  • n has the same meaning as n in Formula (1-1).
  • the hydrogen atom in the following structure may be further substituted with a known substituent such as a hydroxy group or a hydrocarbon group.
  • Y 1 is a group including a structure obtained by removing two or more hydrogen atoms from a structure represented by Formula (V-5)
  • Y 1 is preferably a group represented by Formula (V-5-2).
  • * represents a bonding site to two nitrogen atoms to which Y 1 in Formula (1-1) is bonded.
  • n hydrogen atoms in the following structure are substituted with R 1 in Formula (1-1).
  • n has the same meaning as n in Formula (1-1).
  • the hydrogen atom in the following structure may be further substituted with a known substituent such as a hydroxy group or a hydrocarbon group.
  • Y 1 is a group including a structure obtained by removing two or more hydrogen atoms from a structure represented by Formula (V-6), Y 1 is preferably a group represented by Formula (V-6-2).
  • * represents a bonding site to two nitrogen atoms to which Y 1 in Formula (1-1) is bonded.
  • n hydrogen atoms in the following structure are substituted with R 1 in Formula (1-1).
  • n has the same meaning as n in Formula (1-1).
  • the hydrogen atom in the following structure may be further substituted with a known substituent such as a hydroxy group or a hydrocarbon group.
  • Y 1 is a group including a structure obtained by removing two or more hydrogen atoms from a structure represented by Formula (V-8)
  • Y 1 is preferably a group represented by Formula (V-8-2).
  • * represents a bonding site to two nitrogen atoms to which Y 1 in Formula (1-1) is bonded.
  • n hydrogen atoms in the following structure are substituted with R 1 in Formula (1-1).
  • n has the same meaning as n in Formula (1-1).
  • the hydrogen atom in the following structure may be further substituted with a known substituent such as a hydroxy group or a hydrocarbon group.
  • Y 1 may be a group obtained by removing n hydrogen atoms from a group represented by R 131 in Formula (4) described later.
  • Y 1 does not contain an imide structure in the structure.
  • Y 1 does not contain a urethane bond, a urea bond, and an amide bond in the structure.
  • Y 1 does not contain an ester bond in the structure.
  • Y 1 does not contain an imide structure, a urethane bond, a urea bond, and an amide bond, and it is preferable that Y 1 does not contain an imide structure, a urethane bond, a urea bond, an amide bond, and an ester bond.
  • X 1 and Y 1 in Formula (1-1) each include a structure obtained by removing two or more hydrogen atoms from a structure represented by any one of Formulae (V-1) to (V-4).
  • m is preferably an integer of 0 to 2, and more preferably 0 or 1.
  • m is also one of the preferred aspects of the present invention.
  • n is preferably 1 or 2, and more preferably 2.
  • the first specific resin may include a repeating unit represented by Formula (1-1) in addition to the repeating unit represented by Formula (1-2).
  • the second specific resin includes a repeating unit represented by Formula (1-2).
  • a 1 and A 2 each independently represent an oxygen atom or —NR z —
  • X 1 represents an organic group having 4 or more carbon atoms
  • Y 1 represents an organic group having 4 or more carbon atoms
  • R 1 's each independently represent a group having a polymerizable group
  • R 113 and R 114 each independently represent a hydrogen atom or a monovalent organic group
  • R Z represents a hydrogen atom or a monovalent organic group
  • m represents an integer of 0 to 4
  • n represents an integer of 1 or more.
  • Preferred aspects of X 1 , Y 1 , R 1 , n, and m in Formula (1-2) are the same as the preferred aspects of X 1 , Y 1 , R 1 , n, and m in Formula (1-1) described above.
  • a 1 , A 2 , R 113 , and R 114 in Formula (1-2) are the same as the preferred aspects of A 1 , A 2 , R 113 , and R 114 in Formula (2) described later.
  • the first specific resin may include a repeating unit represented by Formula (1-1) in addition to the repeating unit represented by Formula (1-3).
  • the second specific resin includes a repeating unit represented by Formula (1-3).
  • X 2 represents a (3+m)-valent linking group
  • Y 2 represents a (2+n)-valent linking group
  • R 1 's each independently represent an organic group having a polymerizable group
  • m represents an integer of 0 to 4
  • n represents an integer of 1 or more.
  • examples of X 2 include a linear or branched aliphatic group, a cyclic aliphatic group, an aromatic group, and a group obtained by linking two or more of these groups through a single bond or a linking group, where X 2 is preferably a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a group obtained by combining two or more of these groups through a single bond or a linking group, and X 2 is more preferably an aromatic group having 6 to 20 carbon atoms or a group obtained by combining two or more aromatic groups having 6 to 20 carbon atoms through a single bond or a linking group.
  • the linking group is preferably —O—, —S—, —C( ⁇ O)—, —S( ⁇ O) 2 —, an alkylene group, a halogenated alkylene group, an arylene group, or a linking group obtained by bonding two or more these, and it is more preferably —O—, —S—, an alkylene group, a halogenated alkylene group, an arylene group, or a linking group obtained by bonding two or more these.
  • the alkylene group is preferably an alkylene group having 1 to 20 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms, and still more preferably an alkylene group having 1 to 4 carbon atoms.
  • the halogenated alkylene group is preferably a halogenated alkylene group having 1 to 20 carbon atoms, more preferably a halogenated alkylene group having 1 to 10 carbon atoms, and still more preferably a halogenated alkylene group having 1 to 4 carbon atoms.
  • examples of the halogen atom in the halogenated alkylene group include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, where a fluorine atom is preferable.
  • the halogenated alkylene group may have a hydrogen atom, or all hydrogen atoms in the halogenated alkylene group may be substituted with a halogen atom. However, it is preferable that all hydrogen atoms are substituted with a halogen atom.
  • Examples of the preferred halogenated alkylene group include a (ditrifluoromethyl)methylene group.
  • the arylene group is preferably a phenylene group or a naphthylene group, more preferably a phenylene group, and still more preferably a 1,3-phenylene group or a 1,4-phenylene group.
  • X 2 is preferably derived from a tricarboxylic acid compound in which at least one carboxy group may be subjected to halogenation.
  • the halogenation is preferably chlorination.
  • a compound having three carboxy groups is referred to as a tricarboxylic acid compound.
  • Two carboxy groups of the three carboxy groups of the tricarboxylic acid compound may be subjected to acid anhydrization.
  • Examples of the tricarboxylic acid compound which may be halogenated, which is used in the production of the polyamideimide precursor, include a branched aliphatic, cyclic aliphatic, or aromatic tricarboxylic acid compound.
  • One kind of these tricarboxylic acid compounds may be used alone, or two or more kinds thereof may be used.
  • X 2 does not contain an imide structure in the structure.
  • X 2 does not contain a urethane bond, a urea bond, and an amide bond in the structure.
  • X 2 does not contain an ester bond in the structure.
  • X 1 does not contain an imide structure, a urethane bond, a urea bond, and an amide bond, and it is preferable that X 1 does not contain an imide structure, a urethane bond, a urea bond, an amide bond, and an ester bond.
  • the tricarboxylic acid compound is preferably a tricarboxylic acid compound containing a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a group obtained by combining two or more of these groups through a single bond or a linking group, and more preferably a tricarboxylic acid compound containing an aromatic group having 6 to 20 carbon atoms or a group obtained by combining two or more aromatic groups having 6 to 20 carbon atoms through a single bond or a linking group.
  • the tricarboxylic acid compound examples include 1,2,3-propanetricarboxylic acid, 1,3,5-pentanetricarboxylic acid, citric acid, trimellitic acid, 2,3,6-naphthalenetricarboxylic acid, and a compound in which phthalic acid (or phthalic anhydride) and benzoic acid are linked through a single bond, —O—, —CH 2 —, —C(CH 3 ) 2 —, —C(CF 3 ) 2 —, —SO 2 —, or a phenylene group.
  • These compounds may be a compound (for example, a trimellitic acid anhydride) in which two carboxy groups have been subjected to anhydrization or may be a compound (for example, trimellitic anhydride chloride) in which at least one carboxy group has been halogenated.
  • a compound for example, a trimellitic acid anhydride
  • trimellitic anhydride chloride in which at least one carboxy group has been halogenated.
  • Y 2 , R 1 , n, and m respectively have the same meanings as Y 1 , R 1 , n, and m in Formula (1-1) described above, and preferred aspects thereof are also the same.
  • the specific resin includes a repeating unit represented by Formula (1-3), it is preferable that the specific resin includes a repeating unit represented by Formula (1-3-2).
  • X 2 's each independently represent a (3+m)-valent linking group
  • Y 2 's each independently represent a (2+n)-valent linking group
  • R 1 's each independently represent an organic group having a polymerizable group
  • m's each independently represent an integer of 0 to 4
  • n's each independently represent an integer of 1 or more
  • L 3 represents a divalent linking group.
  • examples of L 3 include a linear or branched aliphatic group, a cyclic aliphatic group, an aromatic group, and a group obtained by linking two or more of these groups through a single bond or a linking group, where L 3 is preferably a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a group obtained by combining two or more of these groups through a single bond or a linking group, and L 3 is more preferably an aromatic group having 6 to 20 carbon atoms or a group obtained by combining two or more aromatic groups having 6 to 20 carbon atoms through a single bond or a linking group.
  • the linking group is preferably —O—, —S—, —C( ⁇ O)—, —S( ⁇ O) 2 —, an alkylene group, a halogenated alkylene group, an arylene group, or a linking group obtained by bonding two or more these, and it is more preferably —O—, —S—, an alkylene group, a halogenated alkylene group, an arylene group, or a linking group obtained by bonding two or more these.
  • the alkylene group is preferably an alkylene group having 1 to 20 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms, and still more preferably an alkylene group having 1 to 4 carbon atoms.
  • the halogenated alkylene group is preferably a halogenated alkylene group having 1 to 20 carbon atoms, more preferably a halogenated alkylene group having 1 to 10 carbon atoms, and still more preferably a halogenated alkylene group having 1 to 4 carbon atoms.
  • examples of the halogen atom in the halogenated alkylene group include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, where a fluorine atom is preferable.
  • the halogenated alkylene group may have a hydrogen atom, or all hydrogen atoms in the halogenated alkylene group may be substituted with a halogen atom. However, it is preferable that all hydrogen atoms are substituted with a halogen atom.
  • Examples of the preferred halogenated alkylene group include a (ditrifluoromethyl)methylene group.
  • the arylene group is preferably a phenylene group or a naphthylene group, more preferably a phenylene group, and still more preferably a 1,3-phenylene group or a 1,4-phenylene group.
  • the first specific resin may include a repeating unit represented by Formula (1-1) in addition to the repeating unit represented by Formula (1-4).
  • the second specific resin includes a repeating unit represented by Formula (1-4).
  • X 2 represents a (3+m)-valent linking group
  • Y 2 represents a (2+n)-valent linking group
  • R 1 's are each independently an organic group having a polymerizable group
  • m represents an integer of 0 to 4
  • n represents an integer of 1 or more
  • a 2 represents an oxygen atom or —NR z —
  • R z represents a hydrogen atom or a monovalent organic group
  • R 113 represents a hydrogen atom or a monovalent organic group.
  • Preferred aspects of X 2 , Y 2 , R 1 , n, and m in Formula (1-4) are the same as the preferred aspects of X 2 , Y 2 , R 1 , n, and m in Formula (1-3) described above.
  • a 2 and R 113 in Formula (1-4) are the same as the preferred aspects of A 2 and R 113 in Formula (2) described later.
  • the specific resin includes a repeating unit represented by Formula (1-4), it is preferable that the specific resin includes a repeating unit represented by Formula (1-4-2).
  • X 2 's each independently represent a (3+m)-valent linking group
  • Y 2 's each independently represent a (2+n)-valent linking group
  • R 1 's each independently represent an organic group having a polymerizable group
  • m's each independently represent an integer of 0 to 4
  • n's each independently represent an integer of 1 or more
  • a 2 's each independently represent an oxygen atom or —NR z —
  • R z 's each independently represent a hydrogen atom or a monovalent organic group
  • R 113 's each independently represent a hydrogen atom or a monovalent organic group
  • L 3 represents a divalent linking group.
  • X 2 , Y 2 , R 1 , m, n, A 2 , and R 113 are the same as the preferred aspects of X 2 , Y 2 , R 1 , m, n, A 2 , and R 113 in Formula (1-4) described above.
  • a preferred aspect of L 3 is the same as the preferred aspect of L 3 in Formula (1-3-2) described above.
  • the first specific resin may include a repeating unit represented by Formula (1-1) in addition to the repeating unit represented by Formula (1-5).
  • the second specific resin includes a repeating unit represented by Formula (1-5).
  • X 2 represents a (3+m)-valent linking group
  • Y 2 represents a (2+n)-valent linking group
  • R 1 's each independently represent an organic group having a polymerizable group
  • m represents an integer of 0 to 4
  • n represents an integer of 1 or more.
  • the specific resin includes a repeating unit represented by Formula (1-5), it is preferable that the specific resin includes a repeating unit represented by Formula (1-5-2).
  • X 2 's each independently represent a (3+m)-valent linking group
  • Y 2 's each independently represent a (2+n)-valent linking group
  • R 1 's each independently represent an organic group having a polymerizable group
  • m's each independently represent an integer of 0 to 4
  • n's each independently represent an integer of 1 or more
  • L 3 represents a divalent linking group.
  • the first specific resin may include a repeating unit represented by Formula (1-1) in addition to the repeating unit represented by Formula (1-6).
  • the second specific resin includes a repeating unit represented by Formula (1-6).
  • X 2 represents a (3+m)-valent linking group
  • Y 2 represents a (2+n)-valent linking group
  • R 1 's are each independently an organic group having a polymerizable group
  • m represents an integer of 0 to 4
  • n represents an integer of 1 or more
  • a 2 represents an oxygen atom or —NR z —
  • R z represents a hydrogen atom or a monovalent organic group
  • R 113 represents a hydrogen atom or a monovalent organic group.
  • Preferred aspects of X 2 , Y 2 , R 1 , n, and m in Formula (1-6) are the same as the preferred aspects of X 2 , Y 2 , R 1 , n, and m in Formula (1-5) described above.
  • a 2 and R 113 in Formula (1-6) are the same as the preferred aspects of A 2 and R 113 in Formula (2) described later.
  • the specific resin includes a repeating unit represented by Formula (1-6), it is preferable that the specific resin includes a repeating unit represented by Formula (1-6-2).
  • X 2 's each independently represent a (3+m)-valent linking group
  • Y 2 's each independently represent a (2+n)-valent linking group
  • R 1 's each independently represent an organic group having a polymerizable group
  • m's each independently represent an integer of 0 to 4
  • n's each independently represent an integer of 1 or more
  • a 2 's each independently represent an oxygen atom or —NR z —
  • R z 's each independently represent a hydrogen atom or a monovalent organic group
  • R 113 's each independently represent a hydrogen atom or a monovalent organic group
  • L 3 represents a divalent linking group.
  • X 2 , Y 2 , R 1 , m, n, A 2 , and R 113 are the same as the preferred aspects of X 2 , Y 2 , R 1 , m, n, A 2 , and R 113 in Formula (1-6) described above.
  • a preferred aspect of L 3 is the same as the preferred aspect of L 3 in Formula (1-3-2) described above.
  • the specific resin may include a repeating unit represented by Formula (2).
  • the repeating unit corresponding to the repeating unit represented by Formula (1-2) does not correspond to the repeating unit represented by Formula (2).
  • a 1 and A 2 each independently represent an oxygen atom or —NR z —
  • R 111 represents a divalent organic group
  • R 115 represents a tetravalent organic group
  • R 113 and R 114 each independently represent a hydrogen atom or a monovalent organic group
  • R Z represents a hydrogen atom or a monovalent organic group.
  • a 1 and A 2 in Formula (2) each independently represent an oxygen atom or —NR Z —, and an oxygen atom is preferable.
  • R Z represents a hydrogen atom or a monovalent organic group, and a hydrogen atom is preferable.
  • R 111 in Formula (2) represents a divalent organic group.
  • R 111 include groups described in paragraphs 0042 to 0053 of JP2023-003421A. These descriptions are incorporated into the present specification.
  • R 111 is also preferably a group including a structure obtained by removing two or more hydrogen atoms from the structure represented by any one of Formula (V-1) to Formula (V-10) described above, the group having no bonding site to R 1 described above.
  • a preferred aspect of such a group is the same as the preferred aspect of the group including a structure obtained by removing two or more hydrogen atoms from the structure represented by any one of Formulae (V-1) to (V-10) in Y 1 included in Formula (1-2), except that the group does not have a bonding site to R 1 .
  • R 115 include a tetracarboxylic acid residue that remains after the removal of the anhydride group from the tetracarboxylic acid dianhydride.
  • the specific resin may contain only one kind of tetracarboxylic acid dianhydride residue or may contain two or more kinds thereof, as a structure corresponding to R 115 .
  • Examples of the tetracarboxylic acid dianhydride include the compounds described in paragraphs 0055 to 0057 of JP2023-003421A. These descriptions are incorporated into the present specification.
  • R 111 is also preferably a group including a structure obtained by removing two or more hydrogen atoms from the structure represented by any one of Formula (V-1) to Formula (V-10) described above, the group having no bonding site to R 1 described above.
  • a preferred aspect of such a group is the same as the preferred aspect of the group including a structure obtained by removing two or more hydrogen atoms from the structure represented by any one of Formulae (V-1) to (V-10) included in X 1 in Formula (1-2), except that the group does not have a bonding site to R 1 .
  • R 111 or R 115 has an OH group. More specifically, examples of R 111 include a residue of a bisaminophenol derivative.
  • R 113 and R 114 in Formula (2) each independently represent a hydrogen atom or a monovalent organic group.
  • R 113 and R 114 include groups described in paragraphs 0058 to 0063 of JP2023-003421A. These descriptions are incorporated into the present specification.
  • the first specific resin and the second specific resin may include a repeating unit represented by Formula (4).
  • the repeating unit corresponding to the repeating unit represented by Formula (1-1) does not correspond to the repeating unit represented by Formula (4).
  • R 131 represents a divalent organic group
  • R 132 represents a tetravalent organic group
  • R 131 represents a divalent organic group.
  • Examples of the divalent organic group include the same one as R 111 in Formula (2), and the same applies to the preferred range thereof.
  • R 131 examples include a diamine residue that remains after the removal of an amino group of a diamine.
  • the diamine examples include an aliphatic, a cyclic aliphatic, and an aromatic diamine. Specific examples thereof include the example of R 111 in Formula (2) which is contained in the polyimide precursor.
  • R 131 is a diamine residue having at least two alkylene glycol units in the main chain from the viewpoint of more effectively suppressing the occurrence of warping during baking. It is more preferably a diamine residue containing, in one molecule, a total of two or more chains of any one or both of the ethylene glycol chain and the propylene glycol chain, and it is still more preferably the above-described diamine which is a diamine residue containing no aromatic ring.
  • Examples of the diamine containing, in one molecule, a total of two or more chains of any one or both of the ethylene glycol chain and the propylene glycol chain include JEFFAMINE (registered trade name) KH-511, ED-600, ED-900, ED-2003, EDR-148, EDR-176, D-200, D-400, D-2000, D-4000 (all product names, manufactured by HUNTSMAN Corporation), 1-(2-(2-(2-aminopropoxy)ethoxy)propoxy)propane-2-amine, and 1-(1-(1-(2-aminopropoxy)propan-2-yl)oxy)propane-2-amine, which are not limited thereto.
  • R 132 represents a tetravalent organic group.
  • examples of the tetravalent organic group include the same one as R 115 in Formula (2), and the same applies to the preferred range thereof.
  • R 115 four bonding partners of the tetravalent organic group exemplified as R 115 are bonded to four —C( ⁇ O)—moieties in Formula (4) to form a fused ring.
  • R 132 examples include a tetracarboxylic acid residue that remains after the removal of the anhydride group from the tetracarboxylic acid dianhydride. Specific examples thereof include the example of R 115 in Formula (2) which is contained in the polyimide precursor. From the viewpoint of the hardness of the organic film, R 132 is preferably an aromatic diamine residue having 1 to 4 aromatic rings.
  • R 131 it is also preferable that an OH group is contained in at least one of R 131 or R 132 .
  • R 131 include 2,2-bis(3-hydroxy-4-aminophenyl)propane, 2,2-bis(3-hydroxy-4-aminophenyl)hexafluoropropane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, and the above (DA-1) to (DA-18), and more preferred examples of R 132 include the above (DAA-1) to (DAA-5).
  • the first specific resin and the second specific resin may include a repeating unit represented by Formula (PAI-2).
  • R 117 represents a trivalent organic group
  • R 111 represents a divalent organic group
  • a 2 represents an oxygen atom or —NH—
  • Z 1 represents an oxygen atom or —NH—
  • R 113 represents a hydrogen atom or a monovalent organic group.
  • examples of R 117 include a linear or branched aliphatic group, a cyclic aliphatic group, an aromatic group, a heteroaromatic group, and a group obtained by linking two or more of these groups through a single bond or a linking group, where R 117 is preferably a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a group obtained by combining two or more of these groups through a single bond or a linking group, and R 117 is more preferably an aromatic group having 6 to 20 carbon atoms or a group obtained by combining two or more aromatic groups having 6 to 20 carbon atoms through a single bond or a linking group.
  • the linking group is preferably —O—, —S—, —C( ⁇ O)—, —S( ⁇ O) 2 —, an alkylene group, a halogenated alkylene group, an arylene group, or a linking group obtained by bonding two or more these, and it is more preferably —O—, —S—, an alkylene group, a halogenated alkylene group, an arylene group, or a linking group obtained by bonding two or more these.
  • the alkylene group is preferably an alkylene group having 1 to 20 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms, and still more preferably an alkylene group having 1 to 4 carbon atoms.
  • the halogenated alkylene group is preferably a halogenated alkylene group having 1 to 20 carbon atoms, more preferably a halogenated alkylene group having 1 to 10 carbon atoms, and still more preferably a halogenated alkylene group having 1 to 4 carbon atoms.
  • examples of the halogen atom in the halogenated alkylene group include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, where a fluorine atom is preferable.
  • the halogenated alkylene group may have a hydrogen atom, or all hydrogen atoms in the halogenated alkylene group may be substituted with a halogen atom. However, it is preferable that all hydrogen atoms are substituted with a halogen atom.
  • Examples of the preferred halogenated alkylene group include a (ditrifluoromethyl)methylene group.
  • the arylene group is preferably a phenylene group or a naphthylene group, more preferably a phenylene group, and still more preferably a 1,3-phenylene group or a 1,4-phenylene group.
  • R 117 is preferably derived from a tricarboxylic acid compound in which at least one carboxy group may be subjected to halogenation.
  • the halogenation is preferably chlorination.
  • a compound having three carboxy groups is referred to as a tricarboxylic acid compound.
  • Two carboxy groups of the three carboxy groups of the tricarboxylic acid compound may be subjected to acid anhydrization.
  • tricarboxylic acid compound examples include a branched aliphatic, cyclic aliphatic, or aromatic tricarboxylic acid compound.
  • One kind of these tricarboxylic acid compounds may be used alone, or two or more kinds thereof may be used.
  • the tricarboxylic acid compound is preferably a tricarboxylic acid compound containing a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a group obtained by combining two or more of these groups through a single bond or a linking group, and more preferably a tricarboxylic acid compound containing an aromatic group having 6 to 20 carbon atoms or a group obtained by combining two or more aromatic groups having 6 to 20 carbon atoms through a single bond or a linking group.
  • the tricarboxylic acid compound examples include 1,2,3-propanetricarboxylic acid, 1,3,5-pentanetricarboxylic acid, citric acid, trimellitic acid, 2,3,6-naphthalenetricarboxylic acid, and a compound in which phthalic acid (or phthalic anhydride) and benzoic acid are linked through a single bond, —O—, —CH 2 —, —C(CH 3 ) 2 —, —C(CF 3 ) 2 —, —SO 2 —, or a phenylene group.
  • These compounds may be a compound (for example, a trimellitic acid anhydride) in which two carboxy groups have been subjected to anhydrization or may be a compound (for example, trimellitic anhydride chloride) in which at least one carboxy group has been halogenated.
  • a compound for example, a trimellitic acid anhydride
  • trimellitic anhydride chloride in which at least one carboxy group has been halogenated.
  • R 111 , A 2 , and R 113 respectively have the same meanings as R 111 , A 2 , and R 113 in Formula (2) described above, and the same applies to the preferred aspects thereof.
  • the specific resin may include a repeating unit represented by Formula (PAI-1).
  • R 116 represents a divalent organic group
  • R 111 represents a divalent organic group
  • examples of R 116 include a linear or branched aliphatic group, a cyclic aliphatic group, an aromatic group, a heteroaromatic group, and a group obtained by linking two or more of these groups through a single bond or a linking group, where R 116 is preferably a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a group obtained by combining two or more of these groups through a single bond or a linking group, and R 116 is more preferably an aromatic group having 6 to 20 carbon atoms or a group obtained by combining two or more aromatic groups having 6 to 20 carbon atoms through a single bond or a linking group.
  • the linking group is preferably —O—, —S—, —C( ⁇ O)—, —S( ⁇ O) 2 —, an alkylene group, a halogenated alkylene group, an arylene group, or a linking group obtained by bonding two or more these, and it is more preferably —O—, —S—, an alkylene group, a halogenated alkylene group, an arylene group, or a linking group obtained by bonding two or more these.
  • the alkylene group is preferably an alkylene group having 1 to 20 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms, and still more preferably an alkylene group having 1 to 4 carbon atoms.
  • the halogenated alkylene group is preferably a halogenated alkylene group having 1 to 20 carbon atoms, more preferably a halogenated alkylene group having 1 to 10 carbon atoms, and still more preferably a halogenated alkylene group having 1 to 4 carbon atoms.
  • examples of the halogen atom in the halogenated alkylene group include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, where a fluorine atom is preferable.
  • the halogenated alkylene group may have a hydrogen atom, or all hydrogen atoms in the halogenated alkylene group may be substituted with a halogen atom. However, it is preferable that all hydrogen atoms are substituted with a halogen atom.
  • Examples of the preferred halogenated alkylene group include a (ditrifluoromethyl)methylene group.
  • the arylene group is preferably a phenylene group or a naphthylene group, more preferably a phenylene group, and still more preferably a 1,3-phenylene group or a 1,4-phenylene group.
  • R 116 is preferably derived from a dicarboxylic acid compound or a dicarboxylic acid dihalide compound.
  • a compound having two carboxy groups is referred to as a dicarboxylic acid compound
  • a compound having two halogenated carboxy groups is referred to as a dicarboxylic acid dihalide compound.
  • the carboxy group in the dicarboxylic acid dihalide compound may be halogenated; however, it is, for example, preferably chlorinated. That is, the dicarboxylic acid dihalide compound is preferably a dicarboxylic acid dichloride compound.
  • One kind of these dicarboxylic acid compounds or dicarboxylic acid dihalide compounds may be used alone, or two or more kinds thereof may be used.
  • the dicarboxylic acid compound or the dicarboxylic acid dihalide compound is preferably a dicarboxylic acid compound or dicarboxylic acid dihalide compound containing a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a group obtained by combining two or more of these groups through a single bond or a linking group, and more preferably a dicarboxylic acid compound or dicarboxylic acid dihalide compound containing an aromatic group having 6 to 20 carbon atoms or a group obtained by combining two or more aromatic groups having 6 to 20 carbon atoms through a single bond or a linking group.
  • dicarboxylic acid compound examples include malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, succinic acid, tetrafluorosuccinic acid, methylsuccinic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, dimethylmethylsuccinic acid, glutaric acid, hexafluoroglutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid, 3,3-dimethylglutaric acid, 3-ethyl-3-methylglutaric acid, adipic acid, octafluoroadipic acid, 3-methyladipic acid, pimelliic acid, 2,2,6,6-tetramethylpimelic acid, suberic acid, dodecafluorosuberic acid, azelaic acid, sebacic acid, hexadecafluo
  • dicarboxylic acid dihalide compound examples include a compound having a structure in which two carboxy groups in the specific examples of the dicarboxylic acid compound are halogenated.
  • R 111 has the same meaning as R 111 in Formula (2) described above, and the same applies to the preferred aspect thereof.
  • the content of the repeating unit represented by Formula (1-1) is preferably 30% by mass or more, more preferably 50% by mass or more, still more preferably 70% by mass or more, and particularly preferably 80% by mass or more with respect to the total mass of the specific resin.
  • the upper limit of the content is not particularly limited, and may be 100% by mass.
  • the total content of the repeating unit represented by Formula (1-1), the repeating unit represented by Formula (1-3), and the repeating unit represented by Formula (1-5) with respect to the total mass of the specific resin is preferably 30% by mass or more, preferably 50% by mass or more, still more preferably 70% by mass or more, and particularly preferably 80% by mass or more.
  • the upper limit of the content is not particularly limited, and may be 100% by mass.
  • the total content of the repeating unit represented by Formula (1-1), the repeating unit represented by Formula (1-3-2), and the repeating unit represented by Formula (1-5-2) with respect to the total mass of the specific resin is preferably 30% by mass or more, preferably 50% by mass or more, still more preferably 70% by mass or more, and particularly preferably 80% by mass or more.
  • the upper limit of the content is not particularly limited, and may be 100% by mass.
  • the specific resin may contain two or more kinds of repeating units contained in the specific resin among the repeating units of the structure. In that case, it is preferable that the total amount is within the above-described range.
  • the total content of the repeating unit represented by Formula (1-1), the repeating unit represented by Formula (1-3), the repeating unit represented by Formula (1-5), and the repeating unit represented by Formula (4) with respect to the total mass of the specific resin is preferably 50% by mass or more, preferably 70% by mass or more, more preferably 80% by mass or more, and particularly preferably 90% by mass or more.
  • the upper limit of the content is not particularly limited, and may be 100% by mass.
  • the total content of the repeating unit represented by Formula (1-1), the repeating unit represented by Formula (1-3-2), the repeating unit represented by Formula (1-5-2), and the repeating unit represented by Formula (4) with respect to the total mass of the specific resin is preferably 50% by mass or more, preferably 70% by mass or more, more preferably 80% by mass or more, and particularly preferably 90% by mass or more.
  • the upper limit of the content is not particularly limited, and may be 100% by mass.
  • the third specific resin may include two or more kinds of repeating units represented by Formula (4) having different structures. In that case, it is preferable that the total amount is within the above-described range.
  • the content of the repeating unit represented by Formula (1-2) is preferably 30% by mass or more, preferably 50% by mass or more, still more preferably 70% by mass or more, and particularly preferably 80% by mass or more with respect to the total mass of the second specific resin.
  • the upper limit of the content is not particularly limited, and may be 100% by mass.
  • the total content of the repeating unit represented by Formula (1-2), the repeating unit represented by Formula (1-4), and the repeating unit represented by Formula (1-6) with respect to the total mass of the second specific resin is preferably 30% by mass or more, preferably 50% by mass or more, still more preferably 70% by mass or more, and particularly preferably 80% by mass or more.
  • the upper limit of the content is not particularly limited, and may be 100% by mass.
  • the total content of the repeating unit represented by Formula (1-2), the repeating unit represented by Formula (1-4-2), and the repeating unit represented by Formula (1-6-2) with respect to the total mass of the second specific resin is preferably 30% by mass or more, preferably 50% by mass or more, still more preferably 70% by mass or more, and particularly preferably 80% by mass or more.
  • the upper limit of the content is not particularly limited, and may be 100% by mass.
  • the specific resin may contain two or more kinds of repeating units contained in the specific resin among the repeating units of the structure. In that case, it is preferable that the total amount is within the above-described range.
  • the total content of the repeating unit represented by Formula (1-2) and the repeating unit represented by Formula (2) is preferably 50% by mass or more, preferably 70% by mass or more, more preferably 80% by mass or more, and particularly preferably 90% by mass or more with respect to the total mass of the second specific resin.
  • the upper limit of the content is not particularly limited, and may be 100% by mass.
  • the first specific resin or the second specific resin includes a repeating unit represented by Formula (2)
  • the first specific resin or the second specific resin may include two or more kinds of repeating units represented by Formula (2) having different structures. In that case, it is preferable that the total amount is within the above-described range.
  • the weight-average molecular weight (Mw) is preferably 3,000 to 100,000.
  • the lower limit of the above-described Mw is preferably 5,000 or more, more preferably 8,000 or more, and still more preferably 10,000 or more.
  • the upper limit of the Mw is preferably 50,000 or less, more preferably 40,000 or less, and still more preferably 25,000 or less.
  • the weight-average molecular weight is set to 3,000 or more, it is possible to improve the breakage resistance of the film after curing.
  • the weight-average molecular weight is particularly preferably 5,000 or more.
  • the number-average molecular weight (Mn) of the polyimide is preferably 1,000 to 40,000, more preferably 2,000 to 30,000, and still more preferably 5,000 to 20,000.
  • the dispersity of the molecular weight of the polyimide is preferably 1.5 or more, more preferably 1.8 or more, and still more preferably 2.0 or more.
  • the upper limit value of the dispersity of the molecular weight of the polyimide is not particularly specified, but is, for example, preferably 7.0 or less, more preferably 6.5 or less, still more preferably 6.0 or less, even more preferably 4.5 or less, and particularly preferably 3.0 or less.
  • the weight-average molecular weight, the number-average molecular weight, and the dispersity of at least one kind of polyimide are in the above ranges. It is also preferable that the weight-average molecular weight, the number-average molecular weight, and the dispersity, calculated by using the plurality of kinds of polyimides as one resin, are within the above ranges.
  • the weight-average molecular weight (Mw) is preferably 5,000 to 100,000, more preferably 10,000 to 50,000, and still more preferably 15,000 to 40,000.
  • the number-average molecular weight (Mn) of the polyimide precursor is preferably 2,000 to 40,000, more preferably 3,000 to 30,000, and still more preferably 4,000 to 20,000.
  • the dispersity of the molecular weight of the polyimide precursor is preferably 1.5 or more, more preferably 1.8 or more, and still more preferably 2.0 or more.
  • the upper limit value of the dispersity of the molecular weight of the polyimide precursor is not particularly specified, but is, for example, preferably 7.0 or less, more preferably 6.5 or less, still more preferably 6.0 or less, even more preferably 4.5 or less, and particularly preferably 3.0 or less.
  • the dispersity of the molecular weight is a value obtained by calculating “weight-average molecular weight/number-average molecular weight”.
  • the weight-average molecular weight, the number-average molecular weight, and the dispersity of at least one kind of polyimide precursor are in the above ranges. Further, it is also preferable that the weight-average molecular weight, the number-average molecular weight, and the dispersity, calculated by using the plurality of kinds of polyimide precursors as one resin, are within the above ranges.
  • an imidization rate of the polyimide (also referred to as “ring closure rate”) is preferably 70% or more, more preferably 80% or more, and still more preferably 90% or more.
  • the upper limit of the imidization rate is not particularly limited, and it may be any imidization rate of 100% or less.
  • the content of the imide structure in the specific resin is preferably 3 mmol/g or less and more preferably 2.5 mmol/g or less.
  • the lower limit of the above-described content is not particularly limited, but can be, for example, 0.5 mmol/g or more.
  • an imidization rate of the polyimide precursor is preferably less than 70%, more preferably 50% or less, still more preferably 20% or less, and particularly preferably 10% or less.
  • the lower limit of the imidization rate is not particularly limited, and it may be any imidization rate of 0% or more.
  • the imidization rate is measured by, for example, the following method.
  • the infrared absorption spectrum of the specific resin is measured, and a peak intensity P1 in the vicinity of 1,377 cm ⁇ 1 , which is the absorption peak derived from the imide structure, is obtained.
  • the specific resin is subjected to a heat treatment at 350° C. for 1 hour, and then the infrared absorption spectrum is measured again to obtain a peak intensity P2 in the vicinity of 1,377 cm ⁇ 1 .
  • the imidization rate of the specific resin can be determined based on the following expression.
  • Imidization rate (%) (peak intensity P1/peak intensity P2) ⁇ 100
  • the specific resin can be obtained by, for example, a method of reacting a tetracarboxylic acid dianhydride with a diamine at a low temperature, a method of reacting a tetracarboxylic acid dianhydride with a diamine at a low temperature to obtain a polyamic acid and subjecting the polyamic acid to esterification by using a condensing agent or an alkylating agent, a method of obtaining a diester with a tetracarboxylic acid dianhydride and alcohol and then reacting the diester with a diamine in the presence of a condensing agent, and a method of obtaining a diester with a tetracarboxylic acid dianhydride and alcohol, subsequently subjecting the rest dicarboxylic acid to acid-halogenation using a halogenating agent, and carrying out reaction with a diamine.
  • a method of obtaining a diester with a tetracarboxylic acid dianhydride and alcohol, subsequently subjecting the rest dicarboxylic acid to acid-halogenation using a halogenating agent, and carrying out a reaction with a diamine is more preferable.
  • condensing agent examples include dicyclohexylcarbodiimide, diisopropylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1-carbonyldioxy-di-1,2,3-benzotriazole, N,N′-disuccinimidyl carbonate, and trifluoroacetic anhydride.
  • alkylating agent examples include N,N-dimethylformamide dimethyl acetal, N,N-dimethylformamide diethyl acetal, N,N-dialkylformamide dialkyl acetal, trimethyl orthoformate, triethyl orthoformate.
  • halogenating agent examples include thionyl chloride, oxalyl chloride, and phosphorus oxychloride.
  • the polyimide in a case where a polyimide is desired to be obtained as the specific resin, the polyimide can be synthesized by a method of completely imidizing the resin obtained by the above method using a known imidization reaction method, a method of introducing a partial imide structure by stopping the imidization reaction in the middle of the reaction, or a method of introducing a partial imide structure by blending a completely imidized polymer and a polyimide precursor thereof.
  • another known method for synthesizing polyimide can also be applied.
  • an organic solvent at the time of reaction.
  • One kind of organic solvent may be used, or two or more kinds thereof may be used.
  • the organic solvent can be appropriately determined depending on the raw material; however, examples thereof include pyridine, diethylene glycol dimethyl ether (diglyme), N-methylpyrrolidone, N-ethylpyrrolidone, ethyl propionate, dimethylacetamide, dimethylformamide, tetrahydrofuran, and ⁇ -butyrolactone.
  • a basic compound in a case of carrying out the reaction.
  • One kind of basic compound may be used, or two or more kinds thereof may be used.
  • the basic compound can be appropriately determined depending on the raw material; however, examples thereof include triethylamine, diisopropylethylamine, pyridine, 1,8-diazabicyclo[5.4.0]undec-7-ene, and N,N-dimethyl-4-aminopyridine.
  • the terminal blocking agent include a monoalcohol, phenol, thiol, thiophenol, and a monoamine. It is more preferable to use a monoalcohol, phenols, or a monoamine from the viewpoint of reactivity and film stability.
  • Examples of the preferred monoalcohol compound include primary alcohol such as methanol, ethanol, propanol, butanol, hexanol, octanol, dodecanol, benzyl alcohol, 2-phenylethanol, 2-methoxyethanol, 2-chloromethanol, and furfuryl alcohol; secondary alcohol such as isopropanol, 2-butanol, cyclohexyl alcohol, cyclopentanol, and 1-methoxy-2-propanol; and tertiary alcohol such as t-butyl alcohol and adamantane alcohol.
  • primary alcohol such as methanol, ethanol, propanol, butanol, hexanol, octanol, dodecanol, benzyl alcohol, 2-phenylethanol, 2-methoxyethanol, 2-chloromethanol, and furfuryl alcohol
  • secondary alcohol such as isopropanol, 2-butanol, cyclohex
  • examples of the preferred compounds of phenols include phenols such as phenol, methoxyphenol, methylphenol, naphthalene-1-ol, naphthalene-2-ol, and hydroxystyrene.
  • examples of the preferred monoamine compound include aniline, 2-ethynyl aniline, 3-ethynyl aniline, 4-ethynyl aniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carbox
  • the preferred terminal blocking agent for the amino group is preferably a carboxylic acid anhydride, a carboxylic acid chloride, a carboxylic acid bromide, a sulfonic acid chloride, sulfonic acid anhydride, a sulfonic acid carboxylic acid anhydride, or the like and more preferably a carboxylic acid anhydride or a carboxylic acid chloride.
  • Examples of the preferred carboxylic acid anhydride compound include acetic anhydride, propionic anhydride, oxalic anhydride, succinic anhydride, maleic acid anhydride, phthalic anhydride, benzoic anhydride, and 5-norbornene-2,3-dicarboxylic acid anhydride.
  • Examples of the preferred carboxylic acid chloride compound include acetyl chloride, acrylic acid chloride, propionyl chloride, methacrylic acid chloride, pivaloyl chloride, cyclohexanecarbonyl chloride, 2-ethylhexanoyl chloride, cinnamoyl chloride, 1-adamantanecarbonyl chloride, heptafluorobutyryl chloride, stearic acid chloride, and benzoyl chloride.
  • an amino acid in a compound having an amino group such as p-aminophenol and a hydroxy group may be reacted with the hydroxy group and a compound that reacts with the hydroxy group, such as 4-(chloromethyl)styrene, after the amino acid is reacted with the terminal of the resin.
  • a polymerizable group can be introduced at the terminal.
  • a step of precipitating a solid may be included. Specifically, it is possible to obtain a specific resin by filtering out a water-absorbing by-product of the dehydration condensing agent that is present together in the reaction solution as necessary, subsequently putting the obtained polymer component in a poor solvent such as water, an aliphatic lower alcohol, or a mixed solution thereof, precipitating the polymer component to be precipitated as a solid, and then carrying out drying. In order to improve the degree of purification, operations such as redissolution, reprecipitation, and drying of the specific resin may be repeated. Further, a step of removing ionic impurities using an ion exchange resin may be included.
  • Specific examples of the specific resin include polyimides (PI-1) to (PI-12), (PA-1), polyimide precursors (SP-1) to (SP-2), (SP-4) to (SP-6), and the like in Examples described later, but the present invention is not limited thereto.
  • the content of the specific resin in the resin composition according to the embodiment of the present invention is preferably 20% by mass or more, more preferably 30% by mass or more, still more preferably 40% by mass or more, even still more preferably 50% by mass or more, and most preferably 60% by mass or more, with respect to the total solid content of the resin composition.
  • the content of the resin in the resin composition according to the embodiment of the present invention is preferably 99.5% by mass or less, more preferably 99% by mass or less, still more preferably 98% by mass or less, still more preferably 97% by mass or less, and even still more preferably 95% by mass or less, with respect to the total solid content of the resin composition.
  • the resin composition according to the embodiment of the present invention may contain only one kind of specific resin or may contain two or more kinds thereof. In a case where two or more kinds thereof are contained, the total amount thereof is preferably within the above range.
  • the resin composition according to the embodiment of the present invention contains at least two kinds of resins.
  • the resin composition according to the embodiment of the present invention may contain in total two or more kinds of the specific resins and other resins described later or may contain two or more kinds of the specific resins; however, it is preferable to include two or more kinds of the specific resins.
  • the resin composition according to the embodiment of the present invention contains two or more kinds of the specific resins, it is preferable to contain, for example, two or more kinds of polyimide precursors which are polyimide precursors in which the structure derived from the dianhydride is different.
  • the resin composition according to the embodiment of the present invention may contain the above-described specific resin and another resin (hereinafter, also simply referred to as “the other resin”) that is different from the specific resin.
  • the other resins include resins different from the specific resin and corresponding to polyimide precursors, polyimides, polybenzoxazole precursors, polybenzoxazole, polyamideimide precursors, polyamideimide, aromatic polyether, phenol resin, polyamide, epoxy resin, polysiloxane, resin including a siloxane structure, (meth)acrylic resin, (meth)acrylamide resin, urethane resin, butyral resin, styryl resin, polyether resin, and polyester resin.
  • polyimide precursors polyimides, polybenzoxazole precursors, polybenzoxazole, polyamideimide precursors, polyamideimide, aromatic polyether, phenol resin, polyamide, epoxy resin, polysiloxane, resin including a siloxane structure, (meth)acrylic resin, (meth)acrylamide resin, urethane resin, butyral resin, styryl resin, polyether resin, and polyester resin.
  • Examples of the other polyimide precursors, the other polyimides, the polybenzoxazole precursors, the polybenzoxazoles, the polyamideimide precursors, and the polyamideimides include the compounds described in paragraphs 0017 to 0138 of WO2022/145355A. The above description is incorporated in the present specification.
  • the aromatic polyether is not particularly limited, but is preferably a polyphenylene ether.
  • the polyphenylene ether preferably includes a repeating unit represented by Formula (PE).
  • R E1 represents a hydrogen atom or a substituent.
  • substituents include a halogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, an amino group which may have a substituent, a nitro group, and a carboxy group.
  • polyphenylene ether is also preferably a compound having a polymerizable group.
  • an epoxy group an oxetanyl group, an oxazolyl group, a methylol group, an alkoxymethyl group, an acyloxymethyl group, a blocked isocyanate group, or a group having an ethylenically unsaturated bond is preferable, and a group having an ethylenically unsaturated bond is more preferable.
  • Examples of the group having an ethylenically unsaturated bond include a vinyl group, an allyl group, an isoallyl group, a 2-methylallyl group, a group (for example, a vinylphenyl group) having an aromatic ring that is directly bonded to a vinyl group, and a (meth)acrylamide group, a (meth)acryloyloxy group, where a vinylphenyl group, a (meth)acrylamide group, or a (meth)acryloyloxy group is preferable, a vinylphenyl group or a (meth)acryloyloxy group is more preferable, and a (meth)acryloyloxy group is still more preferable.
  • the position of the polymerizable group is not particularly limited, but for example, a structure in which the polymerizable group is introduced at the terminal of the main chain is preferable.
  • the polyphenylene ether may include other repeating units.
  • the content of the other repeating units is preferably 30% by mass or less, more preferably 20% by mass or less, and still more preferably 10% by mass or less with respect to the total mass of the polyphenylene ether.
  • the number-average molecular weight of the polyphenylene ether is not particularly limited, but is preferably 500 to 50,000.
  • the lower limit of the number-average molecular weight is preferably 800 or higher, more preferably 1000 or higher, and still more preferably 1500 or higher.
  • the upper limit of the number-average molecular weight is preferably 30,000 or less, more preferably 20,000 or less, and still more preferably 10,000 or less.
  • polyphenylene ether examples include poly(2,6-dimethyl-1,4-phenylene ether), poly(2-methyl-6-ethyl-1,4-phenylene ether), poly(2-methyl-6-phenyl-1,4-phenylene ether), poly(2,6-dichloro-1,4-phenylene ether), a copolymer of 2,6-dimethylphenol and other phenols (for example, 2,3,6-trimethylphenol, 2-methyl-6-butylphenol, and the like), a polyphenylene ether copolymer obtained by coupling 2,6-dimethylphenol with biphenols or bisphenols, and a polyphenylene ether having a linear structure or a branched structure, which is obtained by heating poly(2,6-dimethyl-1,4-phenylene ether) and the like with phenolic compounds such as bisphenols or trisphenols in a toluene solvent in the presence of an organic peroxide and performing a redistribu
  • PPE poly(
  • the content of the other resin is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, still more preferably 1% by mass or more, even still more preferably 2% by mass or more, even still more preferably 5% by mass or more, and even further still more preferably 10% by mass or more, with respect to the total solid content of the resin composition.
  • the content of the other resin in the resin composition according to the embodiment of the present invention is preferably 80% by mass or less, more preferably 75% by mass or less, still more preferably 70% by mass or less, even still more preferably 60% by mass or less, and even further still more preferably 50% by mass or less, with respect to the total solid content of the resin composition.
  • the content of the other resin is a low content
  • the content of the other resin is preferably 20% by mass or less, more preferably 15% by mass or less, still more preferably 10% by mass or less, even still more preferably 5% by mass or less, and even further still more preferably 1% by mass or less, with respect to the total solid content of the resin composition.
  • the lower limit of the content is not particularly limited, and it may be any content of 0% by mass or more.
  • the content of the specific resin with respect to the total content of the specific resin and the other resin is preferably 40% to 90% by mass, more preferably 50% to 80% by mass, and still more preferably 55% to 70% by mass.
  • the resin composition according to the embodiment of the present invention may contain only one kind of the other resin or may contain two or more kinds thereof. In a case where two or more kinds thereof are contained, the total amount thereof is preferably within the above range.
  • the resin composition according to the embodiment of the present invention preferably contains a polymerizable compound.
  • the resin composition according to the embodiment of the present invention preferably contains a photopolymerization initiator as a photosensitizing agent and contains a polymerizable compound.
  • the melting point of the polymerizable compound is preferably 25° C. or lower. By setting the melting point to 25° C. or lower, the coating film is likely to flow during drying and heating, and the flatness of the cured substance can be improved.
  • the polymerizable compound includes a compound having a C log P value of 3.0 or more, and it is more preferable that the polymerizable compound includes a compound having a C log P value of 3.0 or more and having an aromatic ring structure or an aliphatic ring structure with 6 or more carbon atoms.
  • the C log P value of a compound is defined as follows.
  • the octanol-water partition coefficient (log P value) can be measured generally by a flask immersion method described in JIS Japanese Industrial Standard Z7260-107 (2000).
  • the octanol-water partition coefficient (log P value) can also be estimated by a computational chemistry method or an empirical method instead of measurement.
  • a Crippen's fragmentation method J. Chem. Inf. Comput. Sci., 27, 21 (1987)
  • a Viswanadhan's fragmentation method J. Chem. Inf. Comput. Sci., 29, 163 (1989)
  • a Broto's fragmentation method (Eur. J. Med.
  • the C log P value is a value obtained by calculating the common logarithm log P of the 1-octanol/water partition coefficient P
  • a known method or software can be used for calculating the C log P value, but unless otherwise specified, in the present invention, a C log P program incorporated in the system: PCModels of Daylight Chemical Information Systems, Inc. is used.
  • the C log P value is preferably 4.0 or more and more preferably 6.0 or more.
  • the upper limit of the C log P value is not particularly limited, but is preferably 15.0 or less.
  • the above-described aromatic ring structure may be an aromatic hydrocarbon ring or an aromatic heterocyclic ring, but is preferably an aromatic hydrocarbon ring, and more preferably includes a benzene ring.
  • a fused ring such as a fluorene ring is preferable.
  • an aliphatic ring structure with 6 or more carbon atoms an aliphatic ring structure with 6 to 30 carbon atoms is preferable, and an aliphatic ring structure with 6 to 20 carbon atoms is more preferable.
  • Examples of the aliphatic ring structure with 6 or more carbon atoms include a monocyclic ring such as a cyclohexane ring, and a polycyclic ring such as a dicyclopentane ring and a tricyclo[5.2.1.0 2,6 ]decane ring, and a polycyclic ring is preferable.
  • the polymerizable compound having a C log P value of 3.0 or more is preferably a compound containing a group having an ethylenically unsaturated bond, and more preferably a compound containing two or more groups having an ethylenically unsaturated bond.
  • the compound is also preferably a compound having two groups having an ethylenically unsaturated bond.
  • the polymerizable compound having a C log P value of 3.0 or more is preferably a compound corresponding to a radical crosslinking agent described later.
  • polymerizable compound having a C log P value of 3.0 or more include the following compounds, but the polymerizable compound is not limited thereto.
  • Examples of the polymerizable compound include a radical crosslinking agent and another crosslinking agent.
  • the resin composition according to the embodiment of the present invention preferably contains a radical crosslinking agent.
  • the radical crosslinking agent is a compound having a radically polymerizable group.
  • the radically polymerizable group is preferably a group containing an ethylenically unsaturated bond.
  • Examples of the group containing an ethylenically unsaturated bond include a vinyl group, an allyl group, a vinylphenyl group, a (meth)acryloyl group, a maleimide group, and a (meth)acrylamide group.
  • a (meth)acryloyl group, a (meth)acrylamide group, or a vinylphenyl group is preferable, and from the viewpoint of reactivity, a (meth)acryloyl group is more preferable.
  • the radical crosslinking agent is preferably a compound having one or more ethylenically unsaturated bonds; however, a compound having two or more ethylenically unsaturated bonds is more preferable.
  • the radical crosslinking agent may have three or more ethylenically unsaturated bonds.
  • the compound having 2 or more ethylenically unsaturated bonds is preferably a compound having 2 to 15 ethylenically unsaturated bonds, more preferably a compound having 2 to 10 ethylenically unsaturated bonds, and still more preferably a compound having 2 to 6 ethylenically unsaturated bonds.
  • the resin composition according to the embodiment of the present invention preferably contains a compound having two ethylenically unsaturated bonds and a compound having three or more ethylenically unsaturated bonds.
  • the molecular weight of the radical crosslinking agent is preferably 2,000 or less, more preferably 1,500 or less, and still more preferably 900 or less.
  • the lower limit of the molecular weight of the radical crosslinking agent is preferably 100 or more.
  • radical crosslinking agent examples include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, and maleic acid), and esters and amides thereof, where esters between unsaturated carboxylic acids and polyhydric alcohol compounds or amides between unsaturated carboxylic acids and polyvalent amine compounds are preferable.
  • unsaturated carboxylic acids for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, and maleic acid
  • esters and amides thereof where esters between unsaturated carboxylic acids and polyhydric alcohol compounds or amides between unsaturated carboxylic acids and polyvalent amine compounds are preferable.
  • addition reaction products produced by reacting unsaturated carboxylic acid esters or amides, having a nucleophilic substituent such as a hydroxy group, an amino group, or a sulfanyl group, with monofunctional or polyfunctional isocyanates or epoxies, dehydration condensation reaction products produced by reacting the above esters or amides with a monofunctional or polyfunctional carboxylic acid, or the like are also suitably used.
  • the radical crosslinking agent is also preferably a compound having a boiling point of 100° C. or higher under normal pressure.
  • Examples of the compound having a boiling point of 100° C. or higher under normal pressure include the compounds described in paragraph 0203 of WO2021/112189A. The content thereof is incorporated in the present specification.
  • Examples of the preferred radical crosslinking agent other than those described above include the radically polymerizable compounds described in paragraphs 0204 to 0208 of WO2021/112189A. The content thereof is incorporated in the present specification.
  • dipentaerythritol triacrylate (as a commercially available product, KAYARAD D-330 (manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (as a commercially available product, KAYARAD D-320 (manufactured by Nippon Kayaku Co., Ltd.), A-TMMT (manufactured by Shin-Nakamura Chemical Co., Ltd.), dipentaerythritol penta(meth)acrylate (as a commercially available product, KAYARAD D-310 (manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa(meth)acrylate (as a commercially available product, KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.), A-DPH (manufactured by Shin-Nakamura Chemical Co
  • Examples of the commercially available product of the radical crosslinking agent include SR-494 which is a tetrafunctional acrylate having four ethyleneoxy chains, SR-209, 231, and 239 which are a difunctional methacrylate having four ethyleneoxy chains (all of which are manufactured by Sartomer Company Inc.), DPCA-60 which is a hexafunctional acrylate having six pentyleneoxy chains and TPA-330 which is a trifunctional acrylate having three isobutylene oxy chains (all of which are manufactured by Nippon Kayaku Co., Ltd.), UAS-10 and UAB-140 which are a urethane oligomer (all of which are manufactured by Nippon Paper Industries Co., Ltd.), NK Ester M-40G, NK Ester 4G, NK Ester M-9300, NK Ester A-9300, and UA-7200 (all of which are manufactured by Shin-Nakamura Chemical Co., Ltd.), DPHA-40H (manufactured by Nippon Kay
  • the compounds having an amino structure or a sulfide structure in the molecule as described in JP1988-277653A JP-S63-277653A
  • JP1988-260909A JP-S63-260909A
  • JP1989-105238A JP-H01-105238A
  • the radical crosslinking agent may be a radical crosslinking agent having an acid group such as a carboxy group or a phosphoric acid group.
  • the radical crosslinking agent having an acid group is preferably an ester between an aliphatic polyhydroxy compound and an unsaturated carboxylic acid and more preferably a radical crosslinking agent obtained by reacting an unreacted hydroxy group of an aliphatic polyhydroxy compound with a non-aromatic carboxylic acid anhydride to have an acid group.
  • the radical crosslinking agent is particularly preferably a compound in which an aliphatic polyhydroxy compound is pentaerythritol or dipentaerythritol in a radical crosslinking agent having an acid group obtained by reacting an unreacted hydroxy group of the aliphatic polyhydroxy compound with a non-aromatic carboxylic acid anhydride.
  • examples of the commercially available product thereof include M-510 and M-520 as polybasic acid-modified acrylic oligomers which are manufactured by Toagosei Co., Ltd.
  • An acid value of the radical crosslinking agent having an acid group is preferably 0.1 to 300 mgKOH/g and more preferably 1 to 100 mgKOH/g. In a case where the acid value of the radical crosslinking agent is within the above-described range, excellent manufacturing handleability is exhibited, and excellent developability is exhibited. In addition, good polymerization properties are exhibited. The acid value is measured in accordance with the description of JIS K 0070: 1992.
  • difunctional methacrylate or acrylate from the viewpoint of pattern resolution and film elasticity.
  • the following compound can be used; triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate, polyethylene glycol (PEG) 200 diacrylate, PEG 200 dimethacrylate, PEG 600 diacrylate, PEG 600 dimethacrylate, polytetraethylene glycol diacrylate, polytetraethylene glycol dimethacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, 3-methyl-1, 5-pentanediol diacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, dimethylol-tricyclodecanediacrylate, dimethylol-tricyclodecanedimethacrylate, a diacrylate of an ethylene glycol (P
  • the PEG 200 diacrylate refers to a polyethylene glycol diacrylate having a polyethylene glycol chain Formula weight of about 200.
  • a monofunctional radical crosslinking agent can be preferably used as the radical crosslinking agent from the viewpoint of suppressing the warping of the pattern (cured substance).
  • (meth)acrylic acid derivatives such as n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate; butoxyethyl (meth)acrylate, carbitol (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, N-methylol (meth)acrylamide, glycidyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, and polypropylene glycol mono(meth)acrylate, N-vinyl compounds such as N-vinylpyrrolidone and N-vinyl
  • examples of the bi- or higher functional radical crosslinking agent include allyl compounds such as diallyl phthalate and triallyl trimellitate.
  • the content of the radical crosslinking agent is preferably more than 0% by mass and 60% by mass or less with respect to the total solid content of the resin composition.
  • the lower limit is more preferably 5% by mass or more and still more preferably 10% by mass or more.
  • the upper limit thereof is more preferably 50% by mass or less and still more preferably 30% by mass or less.
  • One kind of radical crosslinking agent may be used alone, or two or more kinds thereof may be mixedly used. In a case where two or more kinds thereof are used in combination, the total amount thereof is preferably in the above range.
  • the resin composition according to the embodiment of the present invention also preferably contains another crosslinking agent different from the radical crosslinking agent described above.
  • the other crosslinking agent refers to a crosslinking agent other than the above-described radical crosslinking agent, where it is preferably a compound having a plurality of groups, in the molecule, which accelerates a reaction of forming a covalent bond between other compounds in the composition or reaction products thereof, by the photosensitization of the above-described photoacid generator or photobase generator, and more preferably a compound having a plurality of groups, in the molecule, which accelerates a reaction of forming a covalent bond between other compounds in the composition or reaction products thereof, by the action of the acid or the base.
  • the acid or the base is preferably an acid or a base, which is generated from a photoacid generator or a photobase generator in the exposure step.
  • crosslinking agent examples include the compounds described in paragraphs 0179 to 0207 of WO2022/145355A. The above description is incorporated in the present specification.
  • the content of the polymerizable compound is preferably more than 0% by mass and 60% by mass or less with respect to the total solid content of the resin composition.
  • the lower limit is more preferably 5% by mass or more and still more preferably 10% by mass or more.
  • the upper limit thereof is more preferably 50% by mass or less and still more preferably 30% by mass or less.
  • One kind of the polymerizable compound may be used alone, or two or more kinds thereof may be mixed and used. In a case where two or more kinds thereof are used in combination, the total amount thereof is preferably in the above range.
  • the resin composition according to the embodiment of the present invention contains a photosensitizing agent.
  • Examples of the photosensitizing agent include a photopolymerization initiator and a photoacid generator, where a photopolymerization initiator is preferable.
  • the resin composition according to the embodiment of the present invention preferably includes a photopolymerization initiator.
  • the photopolymerization initiator is preferably a photoradical polymerization initiator.
  • the photoradical polymerization initiator is not particularly limited and can be appropriately selected from publicly known photoradical polymerization initiators.
  • a photoradical polymerization initiator having photosensitivity to rays ranging from the ultraviolet ray range to the visible light range is preferable.
  • it may be an activator that acts with a sensitizing agent to generate an active radical.
  • the photoradical polymerization initiator preferably contains at least one compound having a molar absorption coefficient of at least about 50 L-mol-1 cm ⁇ 1 within a range of a wavelength of about 240 to 800 nm (preferably 330 to 500 nm).
  • the molar absorption coefficient of a compound can be measured using a well-publicly known method. For example, it is preferable to carry out a measurement at a concentration of 0.01 g/L using an ethyl acetate solvent with an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian Medical Systems, Inc.).
  • a photoradical polymerization initiator well-known compounds can be optionally used.
  • examples thereof include a halogenated hydrocarbon derivative (for example, a compound having a triazine skeleton, a compound having an oxadiazole skeleton, or a compound having a trihalomethyl group), an acylphosphine compound such as an acylphosphine oxide, hexaarylbiimidazole, an oxime compound such as an oxime derivative, an organic peroxide, a thio compound, a ketone compound, an aromatic onium salt, a keto oxime ether, an ⁇ -amino ketone compound such as aminoacetophenone, an ⁇ -hydroxy ketone compound such as hydroxyacetophenone, an azo-based compound, an azide compound, a metallocene compound, an organic boron compound, and an iron arene complex.
  • a halogenated hydrocarbon derivative for example, a compound having a
  • Examples of the ketone compound include compounds described in paragraph 0087 of JP2015-087611A, the content of which is incorporated in the present specification.
  • KAYACURE DETX-S manufactured by Nippon Kayaku Co., Ltd. is also suitably used.
  • a hydroxyacetophenone compound, an aminoacetophenone compound, and an acylphosphine compound can be suitably used as the photoradical polymerization initiator. More specifically, for example, the aminoacetophenone-based initiator described in JP1998-291969A (JP-H10-291969A) and the acylphosphine oxide-based initiator described in JP4225898B can be used, the contents of which are incorporated in the present specification.
  • Omnirad 184 Omnirad 1173, Omnirad 2959, Omnirad 127 (all of which are manufactured by IGM Resins B.V.), IRGACURE 184 (IRGACURE is a registered trademark), DAROCUR 1173, IRGACURE 500, IRGACURE-2959, and IRGACURE 127 (all of which are manufactured by BASF SE) can be used.
  • Omnirad 907, Omnirad 369, Omnirad 369E, Omnirad 379EG (all of which are manufactured by IGM Resins B.V.), IRGACURE 907, IRGACURE 369, and IRGACURE 379 (all of which are manufactured by BASF SE) can be used.
  • aminoacetophenone-based initiator As the aminoacetophenone-based initiator, the acylphosphine oxide-based initiator, and the metallocene compound, it is also possible to suitably use, for example, the compounds described in paragraphs 0161 to 0163 of WO2021/112189A. The content thereof is incorporated in the present specification.
  • Examples of the more preferred photoradical polymerization initiator include an oxime compound.
  • an oxime compound In a case where an oxime compound is used, exposure latitude can be more effectively improved.
  • the oxime compound is particularly preferable since the oxime compound has a wide exposure latitude (a wide exposure margin) and also works as a photocuring accelerator.
  • oxime compound examples include the compounds described in JP2001-233842A, the compounds described in JP2000-080068A, the compounds described in JP2006-342166A, the compounds described in J. C. S. Perkin II (1979, pp. 1653-1660), the compounds described in J. C. S. Perkin II (1979, pp. 156-162), the compounds described in Journal of Photopolymer Science and Technology (1995, pp.
  • Examples of the preferred oxime compound include compounds having the following structures, 3-(benzoyloxy(imino))butan-2-one, 3-(acetoxy(imino))butan-2-one, 3-(propionyloxy(imino))butan-2-one, 2-(acetoxy(imino))pentan-3-one, 2-(acetoxy(imino))-1-phenylpropan-1-one, 2-(benzoyloxy(imino))-1-phenylpropan-1-one, 3-((4-toluenesulfonyloxy)imino)butan-2-one, and 2-(ethoxycarbonyloxy(imino))-1-phenylpropan-1-one.
  • an oxime compound particularly as a photoradical polymerization initiator.
  • the oxime compound as a photoradical polymerization initiator has a linking group of >C ⁇ N—O—C( ⁇ O)—in the molecule.
  • Examples of the commercially available product of the oxime compound include IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, and IRGACURE OXE 04 (all of which are manufactured by BASF SE), ADEKA OPTOMER N-1919 (manufactured by ADEKA Corporation, the photoradical polymerization initiator 2 described in JP2012-014052A), TR-PBG-304 and TR-PBG-305 (all of which are manufactured by Changzhou Tronly New Electronic Materials Co., Ltd.), ADEKA ARKLS NCI-730, NCI-831, and ADEKA ARKLS NCI-930 (all of which are manufactured by ADEKA Corporation), DFI-091 (manufactured by DAITO CHEMIX Co., Ltd.), and SpeedCure PDO (manufactured by SARTOMER ARKEMA).
  • oxime compounds having the following structures can also be used.
  • the photoradical polymerization initiator it is also possible to use, for example, the oxime compounds having a fluorene ring, which are described in paragraphs 0169 to 0171 of WO2021/112189A, an oxime compound having a skeleton in which at least one benzene ring of a carbazole ring is a naphthalene ring, or an oxime compound having a fluorine atom.
  • oxime compounds having a nitro group which are described in paragraphs 0208 to 0210 of WO2021/020359A, an oxime compound having a benzofuran skeleton, or an oxime compound in which a substituent having a hydroxy group is bonded to a carbazole skeleton.
  • the content thereof is incorporated in the present specification.
  • an oxime compound having an aromatic ring group Ar OX1 in which an electron withdrawing group is introduced into an aromatic ring (hereinafter, also referred to as an oxime compound OX) can also be used.
  • the electron withdrawing group contained in the aromatic ring group Ar OX1 include an acyl group, a nitro group, a trifluoromethyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, and a cyano group.
  • an acyl group or a nitro group is preferable, and due to the reason that a film having excellent light resistance is easily formed, an acyl group is more preferable, and a benzoyl group is still more preferable.
  • the benzoyl group may have a substituent.
  • the substituent is preferably a halogen atom, a cyano group, a nitro group, a hydroxy group, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclic oxy group, an alkenyl group, an alkylsulfanyl group, an arylsulfanyl group, an acyl group, or an amino group, more preferably an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic oxy group, an alkylsulfanyl group, an arylsulfanyl group, or an amino group, and still more preferably an alkoxy group, an alkylsulfanyl group, or an amino group.
  • the oxime compound OX is preferably at least one selected from a compound represented by Formula (OX1) or a compound represented by Formula (OX2), and more preferably a compound represented by Formula (OX2).
  • R X1 represents an alkyl group, an alkenyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclic oxy group, an alkylsulfanyl group, an arylsulfanyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, an acyl group, an acyloxy group, an amino group, a phosphinoyl group, a carbamoyl group, or a sulfamoyl group
  • R X2 represents an alkyl group, an alkenyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, or a heterocyclic oxy group, an alkylsulfanyl group, an arylsulfanyl group, an alkyl
  • R X12 is an electron withdrawing group
  • R X10 , R X11 , R X13 , and R X14 are a hydrogen atom.
  • oxime compound OX examples include the compounds described in paragraph Nos. 0083 to 0105 of JP4600600B, the content of which is incorporated in the present specification.
  • Examples of the particularly preferred oxime compound include the oxime compound having a specific substituent described in JP2007-269779A and the oxime compound having a thioaryl group described in JP2009-191061A, the contents of which are incorporated in the present specification.
  • the photoradical polymerization initiator is preferably a compound selected from the group consisting of a trihalomethyltriazine compound, a benzyl dimethyl ketal compound, an ⁇ -hydroxy ketone compound, an ⁇ -aminoketone compound, an acylphosphine compound, a phosphine oxide compound, a metallocene compound, an oxime compound, a triaryl imidazole dimer, an onium salt compound, a benzothiazole compound, a benzophenone compound, an acetophenone compound and a derivative thereof, a cyclopentadiene-benzene-iron complex and a salt thereof, a halomethyl oxadiazole compound, and a 3-aryl substituted coumarin compound.
  • the photoradical polymerization initiator is a trihalomethyltriazine compound, an ⁇ -aminoketone compound, an acylphosphine compound, a phosphine oxide compound, a metallocene compound, an oxime compound, a triaryl imidazole dimer, an onium salt compound, a benzophenone compound, or an acetophenone compound.
  • the compounds described in paragraphs 0175 to 0179 of WO2021/020359A and the compounds described in paragraphs 0048 to 0055 of WO2015/125469A can also be used, the contents of which are incorporated in the present specification.
  • a photoradical polymerization initiator which is difunctional or tri- or higher functional may be used.
  • two or more radicals are generated from one molecule of the photoradical polymerization initiator, and thus good sensitivity is obtained.
  • the crystallinity is reduced, the solubility in a solvent or the like is improved, and the compound is hardly precipitated over time, which makes it possible to improve the temporal stability of the resin composition.
  • the content thereof is preferably 0.1% to 30% by mass, more preferably 0.1% to 20% by mass, still more preferably 0.5% to 15% by mass, and even still more preferably 1.0% to 10% by mass with respect to the total solid content of the resin composition.
  • Only one kind of photopolymerization initiator may be contained, or two or more kinds thereof may be contained.
  • the total amount thereof is preferably within the above-described range.
  • photopolymerization initiator may also function as a thermal polymerization initiator, crosslinking with the photopolymerization initiator may be further allowed to proceed by heating an oven, a hot plate, or the like.
  • the resin composition may contain a sensitizing agent.
  • the sensitizing agent absorbs a specific radioactive ray to be in an electronically excited state.
  • the sensitizing agent in the electronically excited state is brought into contact with a thermal radical polymerization initiator, a photoradical polymerization initiator, or the like, to cause actions such as electron migration, energy transfer, and heat generation.
  • a thermal radical polymerization initiator a photoradical polymerization initiator, or the like
  • the thermal radical polymerization and the photoradical polymerization initiator undergo a chemical change and decompose to generate a radical, an acid, or a base.
  • a benzophenone-based, a Michler's ketone-based, a coumarin-based, a pyrazole azo-based, an anilino azo-based, a triphenylmethane-based, an anthraquinone-based, an anthracene-based, an anthrapylidene-based, a benzylidene-based, an oxonol-based, a pyrazolotriazole azo-based, a pyridone azo-based, a cyanine-based, a phenothiazine-based, a pyrrolopyrazole azomethine-based, a xanthene-based, a phthalocyanine-based, a benzopyran-based, and an indigo-based compound can be used.
  • sensitizing agent examples include, Michler's ketone, 4,4′-bis(diethylamino)benzophenone, 2,5-bis(4′-diethylaminobenzal)cyclopentane, 2,6-bis(4′-diethylaminobenzal)cyclohexanone, 2,6-bis(4′-diethylaminobenzal)-4-methylcyclohexanone, 4,4′-bis(dimethylamino)chalcone, 4,4′-bis(diethylamino)chalcone, p-dimethylaminocinnamylidene indanone, p-dimethylamino benzylidene indanone, 2-(p-dimethylaminophenylbiphenylene)-benzothiazole, 2-(p-dimethylaminophenylvinylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)isonaphtothiazole
  • sensitizing dyes may be used.
  • the content of the sensitizing agent is preferably 0.01% to 20% by mass, more preferably 0.1% to 15% by mass, and still more preferably 0.5% to 10% by mass with respect to the total solid content of the resin composition.
  • One kind of sensitizing agent may be used alone, or two or more kinds thereof may be used in combination.
  • the resin composition according to the embodiment of the present invention may contain a chain transfer agent.
  • the chain transfer agent is defined, for example, in Polymer Dictionary, 3rd Edition, pp. 683 to 684 (edited by The Society of Polymer Science, 2005).
  • the chain transfer agent for example, the following compound is used; a group of compounds having —S—S—, —SO 2 —S—, —N—O—, SH, PH, SiH, or GeH in the molecule, or a dithiobenzoate compound, a trithiocarbonate compound, dithiocarbamate, or a xanthate compound, which has a thiocarbonylthio group that is used for the reversible addition fragmentation chain transfer (RAFT) polymerization.
  • RAFT reversible addition fragmentation chain transfer
  • the content of the chain transfer agent is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, and still more preferably 0.5 to 5 parts by mass, with respect to 100 parts by mass of the total solid content of the resin composition.
  • Only one kind of chain transfer agent may be used alone, or two or more kinds thereof may be used. In a case where two or more kinds of chain transfer agents are used, the total thereof is preferably within the above-described range.
  • the polymerization initiator is preferably a photoacid generator.
  • the photoacid generator is preferably a photoacid generator that generates a radical.
  • the compound is preferably a compound that absorbs light, decomposes the absorbed light to generate a radical, and abstracts hydrogen from a solvent, an acid generator itself, or the like to generate an acid.
  • Examples of the photoacid generator include a quinone diazide compound, an oxime sulfonate compound, an organic halogenated compound, an organic borate compound, a disulfone compound, and an onium salt, and an onium salt is preferable.
  • onium salt examples include a diazonium salt, a phosphonium salt, a sulfonium salt, and an iodonium salt.
  • the onium salt is a salt of a cation having an onium structure and an anion, and the cation and the anion may be or may not be bonded through a covalent bond.
  • the onium salt may be an intramolecular salt having a cation moiety and an anion moiety in the same molecular structure, or may be an intermolecular salt in which a cation molecule and an anion molecule, which are separate molecules, are ionically bonded; however, an intermolecular salt is preferred.
  • the cation moiety or the cation molecule and the anion moiety or the anion molecule may be bonded by the ionic bonding or be dissociated from each other.
  • the sulfonium salt means a salt of a sulfonium cation and an anion.
  • the sulfonium cation is preferably a tertiary sulfonium cation and more preferably a triaryl sulfonium cation.
  • the sulfonium cation is preferably a cation represented by Formula (103).
  • R 8 to R 10 each independently represent a hydrocarbon group.
  • R 8 to R 10 are each independently preferably an alkyl group or an aryl group, more preferably an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms, still more preferably an aryl group having 6 to 12 carbon atoms, and even still more preferably a phenyl group.
  • R 8 to R 10 may have a substituent, and examples of the substituent include a hydroxy group, an aryl group, an alkoxy group, an aryloxy group, an arylcarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, and an acyloxy group.
  • R 8 to R 10 preferably have an alkyl group or an alkoxy group as the substituent, more preferably has a branched alkyl group or an alkoxy group, and still more preferably have a branched alkyl group having 3 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms.
  • R 8 to R 10 may be the same group or different groups; however, from the viewpoint of synthesis compatibility, R 8 to R 10 are preferably the same group.
  • the anion is not particularly limited, and may be selected in consideration of the acid generated.
  • examples of the anion include boron-based anions such as B(C 6 F 5 ) 4 ⁇ and BF 4 ⁇ , phosphorus-based anions such as (Rf) n PF 6-n ⁇ , PF 3 (C 2 F 5 ) 3 ⁇ and PF 6 ⁇ , antimony-based anions such as SbF 6 ⁇ , and other carboxylate anions, sulfonate anions, and the like.
  • the iodonium salt means a salt of an iodonium cation and an anion.
  • anion include the same anions as those in the sulfonium salt described above, and the same applies to the preferred aspect.
  • the iodonium cation is preferably a diaryl iodonium cation.
  • the iodonium cation is preferably a cation represented by Formula (104).
  • R 11 and R 12 each independently represent a hydrocarbon group.
  • R 11 and R 12 are each independently preferably an alkyl group or an aryl group, more preferably an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms, still more preferably an aryl group having 6 to 12 carbon atoms, and even still more preferably a phenyl group.
  • R 11 and R 12 may have a substituent, and examples of the substituent include a hydroxy group, an aryl group, an alkoxy group, an aryloxy group, an arylcarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, and an acyloxy group.
  • R 11 and R 12 preferably have an alkyl group or an alkoxy group as the substituent, more preferably have a branched alkyl group or an alkoxy group, and still more preferably have a branched alkyl group having 3 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms.
  • R 11 and R 12 may be the same group or different groups; however, from the viewpoint of synthesis compatibility, R 11 and R 12 are preferably the same group.
  • the phosphonium salt means a salt of a phosphonium cation and an anion.
  • the anion include the same anions as those in the sulfonium salt described above, and the same applies to the preferred aspect.
  • the phosphonium cation is preferably a quaternary phosphonium cation, and examples thereof include a tetraalkylphosphonium cation and a triarylmonoalkylphosphonium cation.
  • the phosphonium cation is preferably a cation represented by Formula (105).
  • R 13 to R 16 each independently represent a hydrogen atom or a hydrocarbon group.
  • R 13 to R 16 are each independently preferably an alkyl group or an aryl group, more preferably an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms, still more preferably an aryl group having 6 to 12 carbon atoms, and even still more preferably a phenyl group.
  • R 13 to R 16 may have a substituent, and examples of the substituent include a hydroxy group, an aryl group, an alkoxy group, an aryloxy group, an arylcarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, and an acyloxy group.
  • R 13 to R 16 preferably have an alkyl group or an alkoxy group as the substituent, more preferably have a branched alkyl group or an alkoxy group, and still more preferably have a branched alkyl group having 3 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms.
  • R 13 to R 16 may be the same group or different groups; however, from the viewpoint of synthesis compatibility, R 13 to R 16 are preferably the same group.
  • the content of the photoacid generator is preferably 0.1% to 20% by mass, more preferably 0.5% to 18% by mass, still more preferably 0.5% to 10% by mass, even more preferably 0.5% to 3% by mass, and even still more preferably 0.5% to 1.2% by mass, with respect to the total solid content of the resin composition.
  • One kind of photoacid generator may be used alone, or a plurality of kinds thereof may be used in combination. In the case of the combination of a plurality of kinds, it is preferable that the total amount thereof is within the above range.
  • a sensitizing agent in combination, it is also preferable to use a sensitizing agent in combination.
  • the resin composition according to the embodiment of the present invention contains two or more kinds of polymerization initiators as the polymerization initiator.
  • the resin composition according to the embodiment of the present invention preferably contains a photopolymerization initiator and a thermal polymerization initiator described later, or contains the above-described photoradical polymerization initiator and the above-described photoacid generator.
  • the content of the thermal polymerization initiator is preferably 20% to 70% by mass and more preferably 30% to 60% by mass with respect to the total content of the photopolymerization initiator and the thermal polymerization initiator.
  • the performance such as resolution may be improved by containing a photoradical polymerization initiator and a photoacid generator.
  • the content of the photoacid generator is preferably 20% to 70% by mass, and more preferably 30% to 60% by mass with respect to the total content of the photopolymerization initiator and the photoacid generator.
  • thermal polymerization initiator examples include a thermal radical polymerization initiator.
  • the thermal radical polymerization initiator is a compound that generates a radical by heat energy and initiates or accelerates a polymerization reaction of a compound having polymerization properties. In a case where a thermal radical polymerization initiator is added, the polymerization reaction of the resin and the polymerizable compound can be allowed to proceed, and thus the solvent resistance can be further improved.
  • thermal radical polymerization initiator examples include compounds described in paragraphs 0074 to 0118 of JP2008-063554A, the content of which is incorporated in the present specification.
  • the content thereof is preferably 0.1% to 30% by mass, more preferably 0.1% to 20% by mass, and still more preferably 0.5% to 15% by mass with respect to the total solid content of the resin composition.
  • the resin composition may contain only one kind of thermal polymerization initiator, or may contain two or more kinds thereof. In a case where two or more kinds of thermal polymerization initiators are contained, the total amount thereof is preferably within the above-described range.
  • the resin composition according to the embodiment of the present invention may contain a base generator.
  • the base generator is a compound that is capable of generating a base under a physical or chemical action.
  • the preferred base generator include a thermal-base generator and a photobase generator.
  • the resin composition contains a precursor of a cyclization resin
  • the resin composition contains a thermal-base generator it is possible to, for example, accelerate the cyclization reaction of the precursor by heating, whereby the mechanical properties and chemical resistance of the cured substance are improved and for example, the performance as an interlayer insulating film for a re-distribution layer, included in a semiconductor package, is improved.
  • the base generator may be an ionic base generator or may be a nonionic base generator.
  • Examples of the base that is generated from the base generator include a secondary amine and a tertiary amine.
  • the base generator is not particularly limited, and a publicly known base generator can be used.
  • the publicly known base generator include a carbamoyloxime compound, a carbamoylhydroxylamine compound, a carbamic acid compound, a formamide compound, an acetamide compound, a carbamate compound, a benzylcarbamate compound, a nitrobenzylcarbamate compound, a sulfonamide compound, an imidazole derivative compound, an aminimide compound, a pyridine derivative compound, an ⁇ -aminoacetophenone derivative compound, a quaternary ammonium salt derivative compound, an iminium salt, a pyridinium salt, an ⁇ -lactone ring derivative compound, a phthalimide derivative compound, and an acyloxyimino compound.
  • Examples of the base generator include the following compounds; however, the base generator is not limited thereto.
  • the molecular weight of the nonionic base generator is preferably 800 or less, more preferably 600 or less, and still more preferably 500 or less.
  • the lower limit thereof is preferably 100 or more, more preferably 200 or more, and still more preferably 300 or more.
  • Examples of the specific preferred compound of the ionic base generator include the compounds described in paragraphs 0148 to 0163 of WO2018/038002A.
  • the base generator is preferably an amine in which an amino group is protected by a t-butoxycarbonyl group.
  • Examples of the amine compound protected by a t-butoxycarbonyl group include ethanolamine, 3-amino-1-propanol, 1-amino-2-propanol, 2-amino-1-propanol, 4-amino-1-butanol, 2-amino-1-butanol, 1-amino-2-butanol, 3-amino-2,2-dimethyl-1-propanol, 4-amino-2-methyl-1-butanol, valinol, 3-amino-1,2-propanediol, 2-amino-1,3-propanediol, tyramine, norephedrine, 2-amino-1-phenyl-1,3-propanediol, 2-aminocyclohexanol, 4-aminocyclohexanol, 4-aminocyclohexanethanol, 4-(2-aminoethyl)cyclohexanol, N-methylethanolamine, 3-(
  • the content of the base generator is preferably 0.1 to 50 parts by mass with respect to 100 parts by mass of the resin in the resin composition.
  • the lower limit thereof is more preferably 0.3 parts by mass or more and still more preferably 0.5 parts by mass or more.
  • the upper limit thereof is more preferably 30 parts by mass or less, still more preferably 20 parts by mass or less, even still more preferably 10 parts by mass or less, even further still more preferably 5 parts by mass or less, and particularly preferably 4 parts by mass or less.
  • One kind or two or more kinds of base generators can be used.
  • the total amount is preferably within the above-described range.
  • the resin composition according to the embodiment of the present invention preferably contains a solvent.
  • the solvent any publicly known solvent can be used.
  • the solvent is preferably an organic solvent.
  • the organic solvent include compounds such as esters, ethers, ketones, cyclic hydrocarbons, sulfoxides, amides, ureas, and alcohols.
  • esters include ethyl acetate, n-butyl acetate, isobutyl acetate, hexyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, ⁇ -butyrolactone, ⁇ -caprolactone, ⁇ -valerolactone, ⁇ -valerolactone, alkyl alkyloxyacetate (for example, methyl alkyloxyacetate, ethyl alkyloxyacetate, and butyl alkyloxyacetate (for example, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, and ethyl ethoxyacetate)), 3-alkyloxypropionic acid alkyl esters (for example, methyl
  • Suitable examples of ethers include ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol butyl methyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol dimethyl ether, propylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, di
  • ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, 3-methylcyclohexanone, levoglucosenone, and dihydrolevoglucosenone.
  • Suitable examples of the cyclic hydrocarbon include aromatic hydrocarbons such as toluene, xylene, and anisole, and cyclic terpenes such as limonene.
  • Suitable examples of the sulfoxides include dimethyl sulfoxide.
  • Suitable examples of the amide include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, N,N-dimethylisobutylamide, 3-methoxy-N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide, N-formylmorpholine, and N-acetylmorpholine.
  • Suitable examples of the urea include N,N,N′,N′-tetramethylurea and 1,3-dimethyl-2-imidazolidinone.
  • Examples of the alcohols include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 1-pentanol, 1-hexanol, benzyl alcohol, ethylene glycol monomethyl ether, 1-methoxy-2-propanol, 2-ethoxyethanol, diethylene glycol monoethyl ether, diethylene glycol monohexyl ether, triethylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether, polyethylene glycol monomethyl ether, polypropylene glycol, tetraethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monobenzyl ether, ethylene glycol monophenyl ether, methylphenyl carbinol, n-amyl alcohol, methylamyl alcohol, and diacetone alcohol.
  • the solvent is preferably one solvent selected from methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclopentanone, ⁇ -butyrolactone, ⁇ -valerolactone, 3-methoxy-N,N-dimethylpropionamide, toluene, dimethyl sulfoxide, ethyl carbitol acetate, butyl carbitol acetate, N-methyl-2-pyrrolidone, propylene glycol methyl ether, and propylene glycol methyl ether acetate, as well as levoglucosenone and dihydrolevoglucosenone, or a mixed solvent composed of two or more of these.
  • An aspect in which an amount of about 1% to 10% by mass of toluene with respect to the total mass of the solvent is further added to these combinedly used solvents is also one of the preferred aspects of the present invention.
  • the content of ⁇ -valerolactone with respect to the total mass of the solvent is preferably 50% by mass or more, more preferably 60% by mass or more, and still more preferably 70% by mass or more.
  • the upper limit of the above-described content is not particularly limited, and it may be 100% by mass. The above-described content may be determined in consideration of the solubility or the like of the component contained in the resin composition, such as the specific resin.
  • dimethyl sulfoxide and ⁇ -valerolactone are used in combination, with respect to the total mass of the solvent, it is preferable to contain 60% to 90% by mass of ⁇ -valerolactone and 10% to 40% by mass of dimethyl sulfoxide, it is more preferable to contain 70% to 90% by mass of ⁇ -valerolactone and 10% to 30% by mass of dimethyl sulfoxide, and it is still more preferable to contain 75% to 85% by mass of ⁇ -valerolactone and 15% to 25% by mass of dimethyl sulfoxide.
  • the amount of the solvent is such that, from the viewpoint of coatability, the concentration of the total solid contents of the resin composition according to the embodiment of the present invention is preferably 5% to 80% by mass, more preferably 5% to 75% by mass, still more preferably 10% to 70% by mass, and even still more preferably 20% to 70% by mass.
  • the content of the solvent may be adjusted depending on the desired thickness of the coating film and the coating method. In a case where two or more kinds of solvents are contained, the total thereof is preferably within the above-described range.
  • the resin composition according to the embodiment of the present invention preferably contains a metal adhesiveness improving agent.
  • the metal adhesiveness improving agent include a silane coupling agent having an alkoxysilyl group, an aluminum-based auxiliary adhesive agent, a titanium-based auxiliary adhesive agent, a compound having a sulfonamide structure and a compound having a thiourea structure, a phosphoric acid derivative compound, a 0-ketoester compound, and an amino compound.
  • silane coupling agent examples include the compounds described in paragraph 0316 of WO2021/112189A and the compounds described in paragraphs 0067 to 0078 of JP2018-173573A, the contents of which are incorporated in the present specification.
  • Me represents a methyl group
  • Et represents an ethyl group.
  • examples of R shown below include a structure derived from a blocking agent in a blocked isocyanate group.
  • the blocking agent may be selected depending on the desorption temperature; however, examples thereof include an alcohol compound, a phenol compound, a pyrazole compound, a triazole compound, a lactam compound, and an active methylene compound. It is preferably caprolactam or the like, for example, from the viewpoint of setting the desorption temperature to 160° C. to 180° C. Examples of the commercially available product of such a compound include X-12-1293 (manufactured by Shin-Etsu Chemical Co., Ltd.).
  • Examples of the other silane coupling agent include vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl
  • an oligomer type compound having a plurality of alkoxysilyl groups can also be used as the silane coupling agent.
  • Examples of such an oligomer type compound include a compound containing a repeating unit represented by Formula (S-1).
  • R S1 represents a monovalent organic group
  • R S2 represents a hydrogen atom, a hydroxy group, or an alkoxy group
  • n represents an integer of 0 to 2.
  • R S1 preferably has a structure including a polymerizable group.
  • the polymerizable group include a group having an ethylenically unsaturated bond, an epoxy group, an oxetanyl group, a benzoxazolyl group, a blocked isocyanate group, and an amino group.
  • Examples of the group having an ethylenically unsaturated bond include a vinyl group, an allyl group, an isoallyl group, a 2-methylallyl group, a group (for example, a vinylphenyl group) having an aromatic ring that is directly bonded to a vinyl group, and a (meth)acrylamide group, a (meth)acryloyloxy group, where a vinylphenyl group, a (meth)acrylamide group, or a (meth)acryloyloxy group is preferable, a vinylphenyl group or a (meth)acryloyloxy group is more preferable, and a (meth)acryloyloxy group is still more preferable.
  • R S2 is preferably an alkoxy group, and more preferably a methoxy group or an ethoxy group.
  • n an integer of 0 to 2, and it is preferably 1.
  • structures of a plurality of repeating units represented by Formula (S-1) may be the same, where the plurality of repeating units are contained in the oligomer type compound.
  • At least one repeating unit has n of 1 or 2, it is more preferable that at least two repeating units have n of 1 or 2, and it is still more preferable that at least two repeating units have n of 1.
  • oligomer type compound a commercially available product can be used, and examples thereof include KR-513 (manufactured by Shin-Etsu Chemical Co., Ltd.).
  • aluminum-based auxiliary adhesive agent examples include aluminum tris(ethyl acetoacetate), aluminum tris(acetyl acetate), and ethyl acetoacetate aluminum diisopropylate.
  • the compounds described in paragraphs 0046 to 0049 of JP2014-186186A, and the sulfide-based compounds described in paragraphs 0032 to 0043 of JP2013-072935A can also be used, the contents of which are incorporated in the present specification.
  • the content of the metal adhesiveness improving agent is preferably 0.01 to 30 parts by mass, more preferably 0.1 to 10 parts by mass, and still more preferably 0.5 to 5 parts by mass with respect to 100 parts by mass of the specific resin. In a case where the content is set to be equal to or higher than the above lower limit value, good adhesiveness between a pattern and a metal layer is exhibited, and in a case where the content is set to be equal to or lower than the above upper limit value, good heat resistance of the pattern and good mechanical characteristics are exhibited. Only one kind of metal adhesiveness improving agent may be used, or two or more kinds thereof may be used. In a case where two or more kinds thereof are used, the total content thereof is preferably within the above-described range.
  • the resin composition according to the embodiment of the present invention preferably further contains a migration suppressing agent.
  • a migration suppressing agent for example, in a case where the resin composition is applied to a metal layer (or a metal wiring line) to form a film, it is possible to effectively suppress the migration of metal ions derived from the metal layer (or the metal wiring line) into the film, in a case where a migration suppressing agent is contained.
  • the migration suppressing agent is not particularly limited; however, examples thereof include a compound having a heterocyclic ring (a pyrrole ring, a furan ring, a thiophene ring, an imidazole ring, an oxazole ring, a thiazole ring, a pyrazole ring, an isoxazole ring, an isothiazole ring, a tetrazole ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, a piperidine ring, a piperazine ring, a morpholine ring, a 2H-pyran ring and a 6H-pyran ring, or a triazine ring), a compound having thioureas and a sulfanyl group, a hindered phenol-based compound, a salicylic acid derivative-based compound, and
  • a triazole-based compound such as 1,2,4-triazole, benzotriazole, 3-amino-1,2,4-triazole, or 3,5-diamino-1,2,4-triazole, or a tetrazole-based compound such as 1H-tetrazole, 5-phenyltetrazole or 5-amino-1H-tetrazole.
  • an ion trap agent that captures an anion such as a halogen ion can also be used.
  • the rust inhibitors described in paragraph 0094 of JP2013-015701A, the compounds described in paragraphs 0073 to 0076 of JP2009-283711A, the compounds described in paragraph 0052 of JP2011-059656A, the compounds described in paragraphs 0114, 0116, and 0118 of JP2012-194520A, the compounds described in paragraph 0166 of WO2015/199219A, or the like can be used as the other migration suppressing agents, the contents of which are incorporated in the present specification.
  • the migration suppressing agent include the following compounds.
  • the content of the migration suppressing agent is preferably 0.01% to 5.0% by mass, more preferably 0.05% to 2.0% by mass, and still more preferably 0.1% to 1.0% by mass, with respect to the total solid content of the resin composition.
  • migration suppressing agent Only one kind of migration suppressing agent may be used alone, or two or more kinds thereof may be used. In a case where two or more kinds of migration suppressing agents are used, the total thereof is preferably within the above-described range.
  • the resin composition according to the embodiment of the present invention also preferably contains a compound (a light absorbing agent) having a small absorbance at an exposure wavelength thereof upon exposure.
  • Examples of the light absorbing agent include compounds described in paragraphs 0159 to 0183 of WO2022/202647A and compounds described in paragraphs 0088 to 0108 of JP2019-206689A. The content thereof is incorporated in the present specification.
  • the content of the light absorbing agent with respect to the total solid content of the resin composition according to the embodiment of the present invention is not particularly limited, but is preferably 0.1% to 20% by mass, more preferably 0.5% to 10% by mass, and still more preferably 1% to 5% by mass.
  • the resin composition according to the embodiment of the present invention preferably contains a polymerization inhibitor.
  • the polymerization inhibitor include a phenol-based compound, a quinone-based compound, an amino-based compound, an N-oxyl-free radical-based compound, a nitro-based compound, a nitroso-based compound, a heteroaromatic ring-based compound, and a metal compound.
  • the compound of the polymerization inhibitor include the compounds described in paragraph 0310 of WO2021/112189A, p-hydroquinone, o-hydroquinone, a 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl free radical, phenoxazine, and 1,4,4-trimethyl-2,3-diazabicyclo[3.2.2]nona-2-en-N,N-dioxide. The content thereof is incorporated in the present specification.
  • the content of the polymerization inhibitor is preferably 0.01% to 20% by mass, more preferably 0.02% to 15% by mass, and still more preferably 0.05% to 10% by mass, with respect to the total solid content of the resin composition.
  • the resin composition according to the embodiment of the present invention may contain various additives as necessary, for example, a surfactant, a higher fatty acid derivative, a thermal polymerization initiator, inorganic particles, an ultraviolet absorbing agent, an organic titanium compounds, an antioxidant, a photoacid generator, an aggregation inhibitor, a phenol-based compound, another polymer compound, a plasticizer, and other auxiliary agents (for example, an anti-foaming agent, and a flame retardant) within the scope in which the effect of the present invention is obtained.
  • auxiliary agents for example, an anti-foaming agent, and a flame retardant
  • the inorganic particle include calcium carbonate, calcium phosphate, silica, kaolin, talc, titanium dioxide, alumina, barium sulfate, calcium fluoride, lithium fluoride, zeolite, molybdenum sulfide, and glass.
  • the average particle diameter of the inorganic particles is preferably 0.01 to 2.0 ⁇ m, more preferably 0.02 to 1.5 ⁇ m, still more preferably 0.03 to 1.0 ⁇ m, and particularly preferably 0.04 to 0.5 ⁇ m.
  • the average particle diameter of the inorganic particles is the primary particle diameter and the volume average particle diameter.
  • the volume average particle diameter can be measured by, for example, a dynamic light scattering method with Nanotrac WAVE II EX-150 (manufactured by Nikkiso Co., Ltd.).
  • the measurement can also be carried out by a centrifugal sedimentation light transmission method, an X-ray transmission method, or a laser diffraction/light scattering method.
  • the resin composition contains an organic titanium compound, it is possible to form a resin layer having excellent chemical resistance even in a case where curing is carried out at a low temperature.
  • Examples of the usable organic titanium compound include those in which an organic group is bonded to a titanium atom through a covalent bond or an ionic bond.
  • organic titanium compound examples are described in I) to VII) below.
  • Tetraalkoxytitanium compounds examples thereof include titanium tetra(n-butoxide), titanium tetraethoxide, titanium tetra(2-ethylhexoxide), titanium tetraisobutoxide, titanium tetraisopropoxide, titanium tetramethoxide, titanium tetramethoxypropoxide, titanium tetramethylphenoxide, titanium tetra(n-nonyloxide), titanium tetra(n-propoxide), titanium tetrastearyloxide, and titanium tetrakis[bis ⁇ 2,2-(aryloxymethyl)butoxide ⁇ ].
  • Titanocene compounds examples thereof include pentamethylcyclopentadienyl titanium trimethoxide, bis(i5-2,4-cyclopentadien-1-yl)bis(2,6-difluorophenyl)titanium, and bis( ⁇ 5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium.
  • Monoalkoxytitanium compounds examples thereof include titanium tris(dioctyl phosphate)isopropoxide, and titanium tris(dodecylbenzene sulfonate)isopropoxide.
  • Titanium oxide compounds examples thereof include titanium oxide bis(pentanedionate), titanium oxide bis(tetramethylheptandionate), and phthalocyanine titanium oxide.
  • Titanium tetraacetylacetonate compounds examples thereof include titanium tetraacetylacetonate.
  • Titanate coupling agents examples thereof include isopropyltridodecylbenzenesulfonyl titanate.
  • the organic titanium compound is at least one compound selected from the group consisting of the above-described I) titanium chelate compound, II) tetraalkoxytitanium compound, and III) titanocene compound, from the viewpoint of more favorable chemical resistance.
  • titanium diisopropoxide bis(ethyl acetoacetate), titanium tetra(n-butoxide), or bis( ⁇ 5-2,4-cyclopentadiene-1-yl) bis(2,6-difluoro-3-(1H-pyrrole-1-yl)phenyl)titanium is preferable.
  • a compound represented by Formula (T-1) is contained as the organic titanium compound or instead of the organic titanium compound.
  • M is titanium, zirconium, or hafnium
  • 11 is an integer of 0 to 2
  • 12 is 0 or 1
  • 11+12 ⁇ 2 is an integer of 0 to 2
  • m is an integer of 0 to 4
  • n is an integer of 0 to 2
  • R 11 's are each independently a substituted or unsubstituted cyclopentadienyl group, a substituted or unsubstituted alkoxy group, or a substituted or unsubstituted phenoxy group
  • R 12 is a substituted or unsubstituted hydrocarbon group
  • R 2 's are each independently a group including a structure represented by Formula (T-2)
  • R 3 's are each independently a group including a structure represented by Formula (T-2)
  • X A 's are each independently an oxygen atom or a sulfur atom.
  • M represents titanium from the viewpoint of the storage stability of the composition.
  • m is preferably 2 or 4, and more preferably 2.
  • n is preferably 1 or 2, and more preferably 1.
  • R 11 is preferably a substituted or unsubstituted cyclopentadienyl ligand from the viewpoint of the stability of the specific metal complex.
  • cyclopentadienyl group, the alkoxy group, and the phenoxy group as R 11 may be substituted; however, an aspect in which these are unsubstituted is also one of the preferred aspects of the present invention.
  • R 12 is preferably a hydrocarbon group having 1 to 20 carbon atoms and more preferably a hydrocarbon group having 2 to 10 carbon atoms.
  • the hydrocarbon group as R 12 may be any of an aliphatic hydrocarbon group or an aromatic hydrocarbon group; however, it is preferably an aromatic hydrocarbon group.
  • the aliphatic hydrocarbon group may be a saturated aliphatic hydrocarbon group or an unsaturated aliphatic hydrocarbon group; however, it is preferably a saturated aliphatic hydrocarbon group.
  • the aromatic hydrocarbon group is preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms, more preferably an aromatic hydrocarbon group having 6 to 10 carbon atoms, and still more preferably a phenylene group.
  • the substituent as R 12 is preferably a monovalent substituent, and examples thereof include a halogen atom.
  • R 12 is an aromatic hydrocarbon group, it may have an alkyl group as a substituent.
  • R 12 is preferably an unsubstituted phenylene group.
  • the phenylene group as R 12 is preferably a 1,2-phenylene group.
  • the content thereof is preferably 0.05 to 10 parts by mass and more preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the specific resin.
  • the content thereof is 0.05 parts by mass or more, the heat resistance and the chemical resistance of the cured pattern to be obtained are further improved, and in a case where the content thereof is 10 parts by mass or less, the storage stability of the composition is more excellent.
  • the content thereof is preferably 0.05 to 10 parts by mass and more preferably 0.1 to 2 parts by mass with respect to 100 parts by mass of the specific resin.
  • the content thereof is 0.05 parts by mass or more, the heat resistance and the chemical resistance of the cured pattern to be obtained are further improved, and in a case where the content thereof is 10 parts by mass or less, the storage stability of the composition is more excellent.
  • the viscosity of the resin composition according to the embodiment of the present invention can be adjusted by adjusting the concentration of solid contents of the resin composition. From the viewpoint of the coating film thickness, it is preferably 1,000 mm 2 /s to 12,000 mm 2 /s, more preferably 2,000 mm 2 /s to 10,000 mm 2 /s, and still more preferably 2,500 mm 2 /s to 8,000 mm 2 /s. Within the above range, it is easy to obtain a coating film having high uniformity.
  • the moisture content of the resin composition according to the embodiment of the present invention is preferably less than 2.0% by mass, more preferably less than 1.5% by mass, and still more preferably less than 1.0% by mass. In a case of being less than 2.0%, the storage stability of the resin composition is improved.
  • Examples of the method of maintaining the moisture content include adjusting the humidity under storage conditions and reducing the void ratio of the storage container during storage.
  • the metal content of the resin composition according to the embodiment of the present invention is preferably less than 5 parts per million (ppm) by mass, more preferably less than 1 ppm by mass, and still more preferably less than 0.5 ppm by mass.
  • the metal include sodium, potassium, magnesium, calcium, iron, copper chromium, and nickel, however, a metal contained as a complex of an organic compound and a metal is excluded. In a case where a plurality of metals are contained, the total of these metals is preferably within the above-described range.
  • a method of reducing metal impurities which are unintentionally contained in the resin composition according to the embodiment of the present invention a method of selecting a raw material containing a low metal content as the raw material that constitutes the resin composition according to the embodiment of the present invention, a method of filtering a raw material constituting the resin composition according to the embodiment of the present invention, a method of distilling under the conditions in which the inside of the device is lined with polytetrafluoroethylene or the like to suppress the contamination as little as possible, and the like can be mentioned.
  • the content of halogen atoms is preferably less than 500 ppm by mass, more preferably less than 300 ppm by mass, and still more preferably less than 200 ppm by mass, from the viewpoint of wire corrosiveness.
  • the content in a case of being present in a halogen ion state, is preferably less than 5 ppm by mass, more preferably less than 1 ppm by mass, and still more preferably less than 0.5 ppm by mass.
  • the halogen atom include a chlorine atom and a bromine atom. It is preferable that the total content of the chlorine atom and the bromine atom, or the total content of the chlorine ion and the bromine ion is within the above-described range.
  • Preferred examples of the method of adjusting the content of halogen atoms include ion exchange treatment.
  • a storage container publicly known in the related art can be used as a storage container for the resin composition according to the embodiment of the present invention.
  • a storage container for the intended purpose of suppressing the incorporation of impurities into the raw materials and the resin composition according to the embodiment of the present invention, a multilayer bottle in which an inner wall of a container is composed of six kinds of six layers of resin, and a bottle with six kinds of resin being made as a seven-layer structure are preferably used. Examples of such a container include the container described in JP2015-123351A.
  • the cured substance according to the embodiment of the present invention is a cured substance formed by curing the resin composition.
  • the curing of the resin composition is preferably carried out by heating.
  • the heating temperature is more preferably 120° C. to 400° C., still more preferably 140° C. to 380° C., and particularly preferably 170° C. to 350° C.
  • the form of the cured substance of the resin composition is not particularly limited and can be selected depending on the use application, where the form includes a film shape, a rod shape, a spherical shape, a pellet shape, and the like. In the present invention, the cured substance preferably has a film shape.
  • the shape of the cured substance can also be selected depending on the use application by the pattern processing of the resin composition, where the use application includes the formation of a protective film on a wall surface, formation of via holes for conduction, adjustment of impedance, electrostatic capacity, or internal stress, impartment of heat radiation function, and the like.
  • the film thickness of the cured substance (the film consisting of the cured substance) is preferably 0.5 ⁇ m or more and 150 ⁇ m or less.
  • the shrinkage ratio of the resin composition according to the embodiment of the present invention after curing is preferably 50% or less, more preferably 45% or less, and still more preferably 40% or less.
  • the shrinkage ratio refers to a percentage of a change in the volume of the resin composition before and after curing, and it can be calculated according to the following expression.
  • the imidization reaction rate of the cured substance of the resin composition according to the embodiment of the present invention is preferably 70% or more, more preferably 80% or more, and still more preferably 90% or more. In a case of being 70% or more, a cured substance having excellent mechanical properties may be obtained.
  • the breaking elongation of the cured substance of the resin composition according to the embodiment of the present invention is preferably 30% or more, more preferably 40% or more, and still more preferably 50% or more.
  • the glass transition temperature (Tg) of the cured substance of the resin composition according to the embodiment of the present invention is preferably 180° C. or higher, more preferably 210° C. or higher, and still more preferably 230° C. or higher.
  • the resin composition according to the embodiment of the present invention can be prepared by mixing the above-described components.
  • the mixing method is not particularly limited, and mixing can be carried out by methods publicly known in the related art.
  • Examples of the mixing method include mixing with a stirring blade, mixing with a ball mill, and mixing by rotating a tank.
  • the temperature during the mixing is preferably 10° C. to 30° C., and more preferably 15° C. to 25° C.
  • the filter pore diameter is, for example, preferably 5 ⁇ m or less, more preferably 1 ⁇ m or less, still more preferably 0.5 ⁇ m or less, and even still more preferably 0.1 ⁇ m or less.
  • the material of the filter is preferably polytetrafluoroethylene, polyethylene, or nylon. In a case where the material of the filter is polyethylene, it is more preferable to use high density polyethylene (HDPE).
  • HDPE high density polyethylene
  • a plurality of kinds of filters may be connected in series or in parallel and used.
  • filters having different pore diameters or different materials may be used in combination.
  • the connection aspect include an aspect in which an HDPE filter having a pore diameter of 1 ⁇ m is connected in series as the first stage and an HDPE filter having a pore diameter of 0.2 ⁇ m is connected in series as the second stage.
  • various materials may be filtered a plurality of times. In a case of being filtered a plurality of times, circulation filtration may be used. In addition, filtration may be carried out under pressure.
  • the pressure for pressurization is, for example, preferably 0.01 MPa or more and 1.0 MPa or less, more preferably 0.03 MPa or more and 0.9 MPa or less, still more preferably 0.05 MPa or more and 0.7 MPa or less, and even still more preferably 0.05 MPa or more and 0.5 MPa or less.
  • impurity removal treatment using an adsorbing material may be carried out.
  • the filtration using a filter and the impurity removal treatment using an adsorbing material may be combined.
  • adsorbing material a publicly known adsorbing material can be used. Examples thereof include an inorganic adsorbing material such as silica gel and zeolite and an organic adsorbing material such as activated carbon.
  • a step of placing a bottle filled with the resin composition under reduced pressure to carry out degassing may be provided.
  • the manufacturing method for a cured substance according to the embodiment of the present invention preferably includes a film forming step of applying a resin composition onto a base material to form a film.
  • the manufacturing method for a cured substance more preferably includes the above-described film forming step, an exposure step of selectively exposing the film formed by the film forming step, and a development step of developing the film exposed by the exposure step using a developer to form a pattern.
  • the manufacturing method for a cured substance includes the film forming step, the exposure step, the development step, and at least one of a heating step of heating a pattern obtained by the development step or a post-development exposure step of exposing the pattern obtained by the development step.
  • the manufacturing method for a cured substance includes the above-described film forming step and a step of heating the film.
  • the resin composition according to the embodiment of the present invention can be applied onto a base material, thereby being used in a film forming step of forming a film.
  • the manufacturing method for a cured substance according to the embodiment of the present invention preferably includes a film forming step of applying a resin composition onto a base material to form a film.
  • the kind of the base material can be appropriately determined depending on the use application and is not particularly limited.
  • the base material include a base material for semiconductor production, such as silicon, silicon nitride, polysilicon, silicon oxide, or amorphous silicon, quartz, glass, an optical film, a ceramic material, a vapor-deposited film, a magnetic film, a reflective film, a metal base material (for example, it may be any one of a base material formed from a metal or a base material having a metal layer formed by plating, vapor deposition, or the like) such as Ni, Cu, Cr, or Fe, paper, spin-on-glass (SOG), a thin film transistor (TFT) array base material, a mold base material, and an electrode plate of a plasma display panel (PDP).
  • the base material is preferably a base material for semiconductor production, and more preferably a silicon base material, a Cu base material, or a mold base material.
  • a layer such as an intimate attachment layer made of hexamethyl disilazane (HMDS) or the like, or an oxide layer may be provided on the surface of these base materials.
  • HMDS hexamethyl disilazane
  • the shape of the base material is not particularly limited, and it may be a circular shape or may be a rectangular shape.
  • the size of the base material is, for example, preferably a diameter of 100 to 450 mm and more preferably 200 to 450 mm.
  • the length of the short side is, for example, preferably 100 to 1,000 mm and more preferably 200 to 700 mm.
  • a base material having a plate shape and preferably a base material (a substrate) having a panel shape are used.
  • the resin composition is applied to form a film on a surface of a resin layer (for example, a layer consisting of a cured substance) or on a surface of a metal layer, the resin layer or the metal layer serves as the base material.
  • a resin layer for example, a layer consisting of a cured substance
  • the resin layer or the metal layer serves as the base material.
  • the means for applying the resin composition onto a base material is preferably coating.
  • the means for application include a dip coating method, an air knife coating method, a curtain coating method, a wire bar coating method, a gravure coating method, an extrusion coating method, a spray coating method, a spin coating method, a slit coating method, and an ink jet method. From the viewpoint of the uniformity of the film thickness, a spin coating method, a slit coating method, a spray coating method, or an ink jet method is more preferable, and from the viewpoint of the uniformity of the film thickness and the viewpoint of productivity, a spin coating method or a slit coating method is more preferable.
  • a film having a desired thickness can be obtained by adjusting the concentration of solid contents of the resin composition and application conditions according to the means to be applied.
  • the coating method can be appropriately selected depending on the shape of the base material.
  • a spin coating method, a spray coating method, an ink jet method, or the like is preferable, and in a case where a rectangular base material is used, a slit coating method, a spray coating method, an ink jet method, or the like is preferable.
  • the spin coating method can be applied at a rotation speed of 500 to 3,500 rpm for about 10 seconds to 3 minutes.
  • a step of removing an unnecessary film at the end part of the base material may be carried out.
  • Examples of such a step include edge bead rinsing (EBR) and back rinsing.
  • a pre-wetting step of applying various solvents onto the base material before applying the resin composition onto the base material to improve the wettability of the base material and then applying the resin composition may be adopted.
  • the above film may be subjected to a step (a drying step) of drying the film (or the layer) formed for removing the solvent, after the film forming step (the layer forming step).
  • the manufacturing method for a cured substance according to the embodiment of the present invention may include a drying step of drying the film formed by the film forming step.
  • drying step is carried out after the film forming step and before the exposure step.
  • the drying temperature of the film in the drying step is preferably 50° C. to 150° C., more preferably 70° C. to 130° C., and still more preferably 90° C. to 110° C.
  • the drying may be carried out by reducing the pressure.
  • Examples of the drying time include 30 seconds to 20 minutes, and the drying time is preferably 1 minute to 10 minutes and more preferably 2 minutes to 7 minutes.
  • the film may be subjected to an exposure step of selectively exposing the film.
  • the manufacturing method for a cured substance may include an exposure step of selectively exposing the film formed by the film forming step.
  • the selective exposure means that a part of the film is exposed.
  • an exposed region an exposed portion
  • an unexposed region a non-exposed portion
  • the exposure amount is not particularly limited as long as the resin composition according to the embodiment of the present invention can be cured; however, it is, for example, preferably 50 to 10,000 mJ/cm 2 and more preferably 200 to 8,000 mJ/cm 2 in terms of conversion of exposure energy at a wavelength of 365 nm.
  • the exposure wavelength can be appropriately determined in a range of 190 to 1,000 nm and preferably in a range of 240 to 550 nm.
  • the exposure method is not particularly limited as long as at least a part of the film consisting of the resin composition according to the embodiment of the present invention is exposed; however, examples thereof include exposure using a photo mask and exposure by a laser direct imaging method.
  • the film may be subjected to a step of carrying out heating after the exposure (a post-exposure heating step).
  • the manufacturing method for a cured substance according to the embodiment of the present invention may include a post-exposure heating step of heating the film exposed in the exposure step.
  • the post-exposure heating step can be carried out after the exposure step and before the development step.
  • the heating temperature in the post-exposure heating step is preferably 50° C. to 140° C. and more preferably 60° C. to 120° C.
  • the heating time in the post-exposure heating step is preferably 30 seconds to 300 minutes and more preferably 1 minute to 10 minutes.
  • the temperature rising rate from the temperature at the start of heating to the maximum heating temperature is preferably 1 to 12° C./min, more preferably 2 to 10° C./min, and still more preferably 3 to 10° C./min.
  • the temperature rising rate may be appropriately changed during heating.
  • the heating means in the post-exposure heating step is not particularly limited, and a publicly known hot plate, oven, infrared heater, or the like can be used.
  • an inert gas such as nitrogen, helium, argon, or the like to flow.
  • the exposed film may be subjected to a development step of carrying out development using a developer to form a pattern.
  • the manufacturing method for a cured substance according to the embodiment of the present invention may include a development step of developing the film exposed in the exposure step using a developer to form a pattern.
  • one of the exposed portion and the non-exposed portion of the film is removed, and a pattern is formed.
  • the development in which the non-exposed portion of the film is removed by the development step is referred to as negative-tone development
  • the development in which the exposed portion of the film is removed by the development step is referred to as positive-tone development.
  • Examples of the developer that is used in the development step include a developer containing an alkaline aqueous solution or an organic solvent.
  • examples of the basic compound that can be contained in the alkaline aqueous solution include inorganic alkalis, primary amines, secondary amines, tertiary amines, and a quaternary ammonium salt.
  • the basic compound is preferably tetramethylammonium hydroxide (TMAH), potassium hydroxide, sodium carbonate, sodium hydroxide, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, di-n-butylamine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetrapentylammonium hydroxide, tetrahexylammonium hydroxide, tetraoctylammonium hydroxide, ethyltrimethylammonium hydroxide, butyltrimethylammonium hydroxide, methyltriamylammonium hydroxide, dibutyldipentylammonium hydroxide, dimethylbis(2-hydroxyethy
  • the compounds described in paragraph 0387 of WO2021/112189A can be used as the organic solvent.
  • the content thereof is incorporated in the present specification.
  • suitable examples of the alcohols include methanol, ethanol, propanol, isopropanol, butanol, pentanol, octanol, diethylene glycol, propylene glycol, methyl isobutyl carbinol, and triethylene glycol
  • suitable examples of the amides include N-methylpyrrolidone, N-ethylpyrrolidone, and dimethylformamide.
  • the developer contains an organic solvent
  • one kind of organic solvent can be used, or two or more kinds thereof can be mixedly used.
  • a developer containing at least one selected from the group consisting of cyclopentanone, ⁇ -butyrolactone, dimethyl sulfoxide, N-methyl-2-pyrrolidone, and cyclohexanone is preferable
  • a developer containing at least one selected from the group consisting of cyclopentanone, ⁇ -butyrolactone, and dimethyl sulfoxide is more preferable
  • a developer containing cyclopentanone is particularly preferable.
  • the content of the organic solvent with respect to the total mass of the developer is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 80% by mass or more, and particularly preferably 90% by mass or more.
  • the above content may be 100% by mass.
  • the developer may further contain another component.
  • Examples of the other component include a publicly known surfactant and a publicly known anti-foaming agent.
  • the method of supplying a developer is not particularly limited as long as a desired pattern can be formed, and it includes a method of immersing a base material on which a film has been formed in a developer, puddle development of supplying a developer to a film formed on a base material using a nozzle, and a method of continuously supplying a developer.
  • the kind of nozzle is not particularly limited, and examples thereof include a straight nozzle, a shower nozzle, and a spray nozzle.
  • a method of supplying a developer with a straight nozzle or a method of continuously supplying a developer with a spray nozzle is preferable, and from the viewpoint of the permeability of the developer into the image area, a method of supplying a developer with a spray nozzle is more preferable.
  • a step of spinning the base material to remove the developer from the base material may be adopted, and this step may be repeated a plurality of times.
  • Examples of the method of supplying a developer in the development step include a step of continuously supplying a developer to a base material, a step of keeping a developer in a substantially stationary state on a base material, a step of vibrating a developer on a base material by ultrasonic waves or the like, and a step obtained by combining these steps.
  • the development time is preferably 10 seconds to 10 minutes and more preferably 20 seconds to 5 minutes.
  • the temperature of the developer during development is not particularly determined; however, it is preferably 10° C. to 45° C. and more preferably 18° C. to 30° C.
  • washing (rinsing) of the pattern with a rinsing liquid may be further carried out after the treatment with the developer.
  • a method such as supplying a rinsing liquid before the developer which is in contact with the pattern is completely dried may be adopted.
  • the developer is an alkaline aqueous solution
  • a solvent for example, water, an organic solvent different from the organic solvent contained in the developer
  • Examples of the organic solvent in a case where the rinsing liquid contains an organic solvent include the same organic solvents as the organic solvents exemplified in the above-described case where the developer contains an organic solvent.
  • the organic solvent contained in the rinsing liquid is preferably an organic solvent different from the organic solvent contained in the developer, and it is more preferably an organic solvent having a solubility of the pattern, which is lower than that of the organic solvent contained in the developer.
  • the rinsing liquid contains an organic solvent
  • one kind of organic solvent can be used, or two or more kinds thereof can be mixedly used.
  • the organic solvent is preferably cyclopentanone, ⁇ -butyrolactone, dimethyl sulfoxide, N-methylpyrrolidone, cyclohexanone, PGMEA, or PGME, more preferably cyclopentanone, ⁇ -butyrolactone, dimethyl sulfoxide, PGMEA, or PGME, and still more preferably cyclohexanone or PGMEA.
  • the organic solvent is preferably 50% by mass or more, more preferably 70% by mass or more, and still more preferably 90% by mass or more with respect to the total mass of the rinsing liquid.
  • the organic solvent may be 100% by mass with respect to the total mass of the rinsing liquid.
  • the rinsing liquid may further contain another component.
  • Examples of the other component include a publicly known surfactant and a publicly known anti-foaming agent.
  • the method of supplying a rinsing liquid is not particularly limited as long as a desired pattern can be formed and includes a method of immersing a base material in a rinsing liquid, a method of supplying a rinsing liquid to a base material by liquid filling, a method of supplying a rinsing liquid to a base material with a shower, and a method of continuously supplying a rinsing liquid to a base material by means such as a straight nozzle.
  • a method of supplying a rinsing liquid with a shower nozzle, a straight nozzle, a spray nozzle, or the like there is a method of continuously supplying a rinsing liquid with a spray nozzle is preferable.
  • a method of supplying a rinsing liquid with a spray nozzle is more preferable.
  • the kind of nozzle is not particularly limited, and examples thereof include a straight nozzle, a shower nozzle, and a spray nozzle.
  • the rinsing step is preferably a step of supplying, with a straight nozzle, or continuously supplying a rinsing liquid to the exposed film, and it is more preferably a step of supplying a rinsing liquid with a spray nozzle.
  • a step of continuously supplying a rinsing liquid to a base material, a step of keeping a rinsing liquid in a substantially stationary state on a base material, a step of vibrating a rinsing liquid on the base material by ultrasonic waves or the like, and a step obtained by combining these steps can be adopted.
  • the rinsing time is preferably 10 seconds to 10 minutes and more preferably 20 seconds to 5 minutes.
  • the temperature of the rinsing liquid during rinsing is not particularly determined; however, it is preferably 10° C. to 45° C. and more preferably 18° C. to 30° C.
  • the pattern obtained by the development step may be subjected to a heating step of heating the pattern obtained by the development.
  • the manufacturing method for a cured substance according to the embodiment of the present invention may include a heating step of heating the pattern obtained by the development step.
  • the manufacturing method for a cured substance according to the embodiment of the present invention may include a pattern obtained by another method without carrying out the development step, or a heating step of heating a film obtained by the film forming step.
  • the resin such as the polyimide precursor is cyclized to be a resin such as polyimide.
  • the heating temperature (the maximum heating temperature) in the heating step is preferably 50° C. to 450° C., more preferably 150° C. to 350° C., still more preferably 150° C. to 250° C., even still more preferably 160° C. to 250° C., and particularly preferably 160° C. to 230° C.
  • the heating step is preferably a step of accelerating the cyclization reaction of the polyimide precursor in the pattern under the action of the base or the like generated from the base generator by heating.
  • the heating in the heating step is preferably carried out at a temperature rising rate of 1 to 12° C./min from the temperature at the start of heating to the maximum heating temperature.
  • the temperature rising rate is more preferably 2 to 10° C./min and still more preferably 3 to 10° C./min.
  • the above temperature rising rate is set to 1° C./min or higher, the excessive volatilization of the acid or solvent can be prevented while securing productivity, and in a case where the above temperature rising rate is to 12° C./min or lower, the residual stress of the cured substance can be relaxed.
  • the heating is preferably carried out at a temperature rising rate of 1 to 8° C./sec from the temperature at the start of heating to the maximum heating temperature, more preferably 2 to 7° C./sec, and still more preferably 3 to 6° C./sec.
  • the temperature at the start of heating is preferably 20° C. to 150° C., more preferably 20° C. to 130° C., and still more preferably 25° C. to 120° C.
  • the temperature at the start of heating refers to a temperature at which the step of heating to the maximum heating temperature is started.
  • the temperature at the start of heating is the temperature of the film (the layer) after drying, and for example, it is preferable to raise the temperature from a temperature lower by 30° C. to 200° C. than the boiling point of the solvent contained in the resin composition.
  • the heating time (the heating time at the maximum heating temperature) is preferably 5 to 360 minutes, more preferably 10 to 300 minutes, and still more preferably 15 to 240 minutes.
  • the heating temperature is preferably 30° C. or higher, more preferably 80° C. or higher, still more preferably 100° C. or higher, and particularly preferably 120° C. or higher, from the viewpoint of adhesiveness between layers.
  • the upper limit of the heating temperature is preferably 350° C. or lower, more preferably 250° C. or lower, and still more preferably 240° C. or lower.
  • the heating may be carried out stepwise. For example, a step in which the temperature is raised from 25° C. to 120° C. at 3° C./min, held at 120° C. for 60 minutes, raised from 120° C. to 180° C. at 2° C./min, and held at 180° C. for 120 minutes, may be carried out.
  • a step in which the temperature is raised from 25° C. to 120° C. at 3° C./min, held at 120° C. for 60 minutes, raised from 120° C. to 180° C. at 2° C./min, and held at 180° C. for 120 minutes may be carried out.
  • the pretreatment step may be carried out for a short time of about 10 seconds to 2 hours and more preferably 15 seconds to 30 minutes.
  • the pretreatment step may be carried out as a step of two or more stages, for example, a first stage pretreatment step may be carried out in a range of 100° C. to 150° C., and then a second stage pretreatment step may be carried out in a range of 150° C. to 200° C.
  • cooling may be carried out after heating, and the cooling rate, in this case, is preferably 1 to 5° C./min.
  • the heating step is carried out in an atmosphere of a low oxygen concentration, for example, by allowing an inert gas such as nitrogen, helium, argon, or the like to flow, or carrying out heating under reduced pressure.
  • the oxygen concentration is preferably 50 ppm (volume ratio) or lower, and more preferably 20 ppm (volume ratio) or lower.
  • the heating means in the heating step is not particularly limited; however, examples thereof include a hot plate, an infrared furnace, an electric heating oven, a hot air oven, and an infrared oven.
  • the pattern obtained by the development step may be subjected to a post-development exposure step of exposing the pattern after the development step, instead of the heating step or in addition to the heating step.
  • the manufacturing method for a cured substance according to the embodiment of the present invention may include a post-development exposure step of exposing the pattern obtained by the development step.
  • the manufacturing method for a cured substance according to the embodiment of the present invention may include the heating step and the post-development exposure step or may include only one of the heating step and the post-development exposure step.
  • the post-development exposure step it is possible to accelerate, for example, a reaction in which the cyclization of a polyimide precursor or the like proceeds by photosensitization of a photobase generator, a reaction in which the elimination of an acid-decomposable group proceeds by photosensitization of a photoacid generator.
  • the post-development exposure step it is sufficient that at least a part of the pattern obtained in the development step is exposed; however, it is preferable that the whole of the above pattern is exposed.
  • the post-development exposure step can be carried out using, for example, the light source in the above-described exposure step, and it is preferable to use broadband light.
  • the pattern (preferably a pattern that has been subjected to at least one of the heating step or the post-development exposure step) obtained by the development step may be subjected to a metal layer forming step of forming a metal layer on the pattern.
  • metal layer existing metal kinds can be used without particular limitations. Examples thereof include copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, tungsten, tin, silver, and an alloy including these metals, where copper or aluminum is more preferable, and copper is still more preferable.
  • the forming method for the metal layer is not particularly limited, and the existing method can be applied.
  • the methods described in JP2007-157879A, JP2001-521288A, JP2004-214501A, JP2004-101850A, U.S. Pat. No. 7,888,181B2, and U.S. Pat. No. 9,177,926B2 can be used.
  • photolithography, physical vapor deposition method (PVD), chemical vapor phase growth method (CVD), lift-off, electrolytic plating, electroless plating, etching, printing, and a method obtained by combining these may be conceivable.
  • the forming method for the metal layer include a patterning method obtained by combining sputtering, photolithography, and etching, and a patterning method combining photolithography and electrolytic plating.
  • Examples of the preferred aspect of the plating include electrolytic plating using a copper sulfate plating liquid or a copper cyanide plating liquid.
  • the thickness of the metal layer at the thickest portion is preferably 0.01 to 50 ⁇ m and more preferably 1 to 10 ⁇ m.
  • Examples of the field to which the manufacturing method for a cured substance according to the embodiment of the present invention or the cured substance according to the embodiment of the present invention can be applied include an insulating film of an electronic device, an interlayer insulating film for a re-distribution layer, and a stress buffer film.
  • the manufacturing method for a cured substance according to the embodiment of the present invention and the cured substance according to the embodiment of the present invention can also be used for the production of board surfaces such as an offset board surface or a screen board surface, for etching of molded parts, for the production of protective lacquers and dielectric layers in electronics, in particular, microelectronics.
  • a laminate according to the embodiment of the present invention refers to a structure body having a plurality of layers consisting of the cured substance according to the embodiment of the present invention.
  • the laminate is a laminate including two or more layers consisting of a cured substance, and it may be a laminate in which three or more layers are laminated.
  • At least one of the two or more layers consisting of a cured substance, which are included in the laminate is a layer consisting of the cured substance according to the embodiment of the present invention, and from the viewpoint of suppressing the shrinkage of the cured substance, the deformation of the cured substance due to the shrinkage, or the like, it is also preferable that all the layers consisting of a cured substance which are included in the laminate are layers consisting of the cured substance according to the embodiment of the present invention.
  • the manufacturing method for a laminate according to the embodiment of the present invention includes the manufacturing method for a cured substance according to the embodiment of the present invention, and it is more preferable to include repeating, a plurality of times, the manufacturing method for a cured substance according to the embodiment of the present invention.
  • the laminate according to the embodiment of the present invention an aspect in which two or more layers of layers consisting of a cured substance are included and a metal layer is provided between any of the layers consisting of the cured substance is preferable.
  • the metal layer is preferably formed in the metal layer forming step.
  • the manufacturing method for a laminate according to the embodiment of the present invention further includes a metal layer forming step of forming a metal layer on a layer consisting of the cured substance, between the manufacturing methods for a cured substance which are carried out a plurality of times.
  • the preferred aspect of the metal layer forming step is as described above.
  • Examples of the preferred laminate include a laminate including at least a layer structure in which three layers of a layer consisting of a first cured substance, a metal layer, and a layer consisting of a second cured substance are laminated in order.
  • both the layer consisting of the first cured substance and the layer consisting of the second cured substance are layers consisting of the cured substance according to the embodiment of the present invention.
  • the resin composition according to the embodiment of the present invention which is used for forming a layer consisting of the first cured substance and the resin composition according to the embodiment of the present invention which is used for forming a layer consisting of the second cured substance may have the same composition or may have compositions different from each other.
  • the metal layer in the laminate according to the embodiment of the present invention is preferably used as the metal wiring line of the re-distribution layer or the like.
  • the manufacturing method for a laminate according to the embodiment of the present invention preferably further includes a laminating step.
  • the laminating step is a series of steps including carrying out again, in the following order on the surface of the pattern (the resin layer) or the metal layer, at least one of (a) the film forming step (the layer forming step), (b) the exposure step, (c) the development step, or (d) the heating step and the post-development exposure step.
  • the aspect thereof may be such that at least one of (a) the film forming step or (d) the heating step and the post-development exposure step is repeated.
  • the metal layer forming step may be included after at least one of the heating step or the post-development exposure step of (d). It is needless to say that the laminating step may further include appropriately the above-described drying step or the like.
  • a surface activation treatment step may be further carried out after the exposure step, the heating step, or the metal layer forming step.
  • the surface activation treatment include plasma treatment. Details of the surface activation treatment will be described later.
  • the laminating step is preferably carried out 2 to 20 times and more preferably 2 to 9 times.
  • a configuration having resin layers of 2 or more layers and 20 or fewer layers such as a resin layer/a metal layer/a resin layer/a metal layer/a resin layer/a metal layer, is preferable, and a configuration having resin layers of 2 or more layers and 9 or fewer layers is still more preferable.
  • compositions, shapes, film thicknesses, and the like may be the same or may be different from each other.
  • an aspect in which a metal layer is provided, and then furthermore, a cured substance (a resin layer) of the resin composition according to the embodiment of the present invention is formed to cover the metal layer is particularly preferable.
  • Specific examples thereof include an aspect in which (a) the film forming step, (b) the exposure step, (c) the development step, (d) at least one of the heating step or the post-development exposure step, (e) the metal layer forming step are repeated in this order, and an aspect in which (a) the film forming step, (d) at least one of the heating step or the post-development exposure step, and (e) the metal layer forming step are repeated in order.
  • the resin composition layer (the resin layer) according to the embodiment of the present invention and the metal layer can be alternately laminated.
  • the manufacturing method for a laminate according to the embodiment of the present invention preferably includes a surface activation treatment step of subjecting at least a part of the metal layer or a part of the resin composition layer to a surface activation treatment.
  • the surface activation treatment step is usually carried out after the metal layer forming step (preferably, after at least one of the heating step or the post-development exposure step). However, after the development step, the metal layer forming step may be carried out after the resin composition layer is subjected to the surface activation treatment step.
  • Only at least a part of the metal layer may be subjected to the surface activation treatment, only at least a part of the resin composition layer after the exposure may be subjected to the surface activation treatment, or both at least a part of the metal layer and at least a part of the resin composition layer after the exposure may be subjected to the surface activation treatment. It is preferable to carry out the surface activation treatment on at least a part of the metal layer, and it is preferable to carry out the surface activation treatment on a part or whole of the region of the metal layer having a surface on which the resin composition layer is formed. In a case where a surface of the metal layer is subjected to the surface activation treatment in this manner, it is possible to improve the adhesiveness to the resin composition layer (film) to be provided on the surface thereof.
  • the surface activation treatment is carried out on a part or whole of the resin composition layer (the resin layer) after the exposure.
  • a surface of the resin composition layer is subjected to the surface activation treatment in this manner, it is possible to improve the adhesiveness to a metal layer or a resin layer to be provided on the surface that has been subjected to the surface activation treatment.
  • the resin composition layer is cured, such as in a case where negative-tone development is carried out, it is less likely to be damaged by the surface treatment, and thus the adhesiveness is likely to be improved.
  • the surface activation treatment can be carried out, for example, according to the method described in paragraph 0415 of WO2021/112189A. The content thereof is incorporated in the present specification.
  • the present invention also discloses a semiconductor device, which includes the cured substance according to the embodiment of the present invention or the laminate.
  • the present invention also discloses a manufacturing method for a semiconductor device, which includes the manufacturing method for a cured substance according to the embodiment of the present invention or the manufacturing method for a laminate according to the embodiment of the present invention.
  • the resin was subjected to reslurrying with 1 L of water, filtered, reslurried again with 1 L of methanol, filtered, and dried at 40° C. for 10 hours under reduced pressure. Subsequently, the resin dried as described above was dissolved in 250 g of tetrahydrofuran, 40 g of an ion exchange resin (MB-1: manufactured by ORGANO CORPORATION) was added thereto, the mixture was stirred for 4 hours, the ion exchange resin was filtered and removed, and then the polyimide resin was precipitated in 2 L of methanol and stirred for 15 minutes. The polyimide resin was filtered and acquired, and dried at 45° C. for 1 day under reduced pressure to obtain polyimide (PI-1).
  • PI-1 polyimide
  • the obtained polyimide (PI-1) had a weight-average molecular weight of 19,600 and a number-average molecular weight of 7,700.
  • the polyimide (PI-1) is a resin having a repeating unit represented by Formula (PI-1).
  • the structure of the repeating unit was determined from a 1 H-NMR spectrum. In the following structures, the subscripts of the repeating units represent the content molar ratio of the respective repeating units.
  • Polyimides (PI-2) to (PI-12) were synthesized in the same method as in Synthesis Example PI-1, except that the raw materials were appropriately changed.
  • Each of the polyimides (PI-2) to (PI-12) is a resin having a repeating unit represented by Formulae (PI-2) to (PI-12).
  • the structure of each repeating unit was determined from a 1 H-NMR spectrum.
  • the weight-average molecular weight (Mw) and the number-average molecular weight (Mn) of each resin are shown in the table below. In the following structures, the subscripts of the repeating units represent the content molar ratio of the respective repeating units.
  • Polyamideimide (PA-1) was synthesized in the same method as in Synthesis Example PI-1, except that the acid anhydride and the diamine used as raw materials were changed.
  • the weight-average molecular weight of the obtained polyamideimide (PA-1) was 9,500, and the number-average molecular weight thereof was 4,600.
  • the polyamideimide (PA-1) is a resin having a repeating unit represented by Formula (PA-1).
  • the structure of the repeating unit was determined from a 1 H-NMR spectrum. In the following structures, the subscripts of the repeating units represent the content molar ratio of the respective repeating units.
  • Polyamideimide (PA-2) was synthesized in the same method as in the synthesis of the polyamideimide (PA-1), except that the raw materials were changed.
  • the polyamideimide (PA-2) had a weight-average molecular weight of 13,500 and a number-average molecular weight of 6,100.
  • the polyamideimide (PA-2) is a resin having a repeating unit represented by Formula (PA-2).
  • the structure of the repeating unit was determined from a 1 H-NMR spectrum. In the following structures, the subscripts of the repeating units represent the content molar ratio of the respective repeating units.
  • the polyimide precursor resin was precipitated by adding 4 L of water and the water-polyimide precursor resin mixture was stirred for 15 minutes at a speed of 500 rpm.
  • the polyimide precursor resin was filtered and acquired, and then the mixture was stirred again in 4 L of water for 30 minutes, filtered again, and dried at 40° C. for 2 days.
  • the resin dried as described above was dissolved in 200 g of tetrahydrofuran, 50 g of an ion exchange resin (MB-1: manufactured by ORGANO CORPORATION) was added thereto, and the mixture was stirred for 6 hours.
  • the polyimide precursor resin was precipitated by adding 4 L of water and the water-polyimide precursor resin mixture was stirred for 15 minutes at a speed of 500 rpm.
  • the polyimide precursor resin was filtered and acquired, and dried at 45° C. for 2 days under reduced pressure to obtain a polyimide precursor (SP-1).
  • the weight-average molecular weight of the obtained polyimide precursor SP-1 was 10,500, and the number-average molecular weight thereof was 3,400.
  • the polyimide precursor (SP-1) is a resin having a repeating unit represented by Formula (SP-1). The structure of the repeating unit was determined from a 1 H-NMR spectrum.
  • Polyimide precursors (SP-2) and (SP-4) to (SP-6) were synthesized in the same method as in Synthesis Example SP-1, except that the raw materials were appropriately changed.
  • the polyimide precursors (SP-2) and (SP-4) to (SP-6) are each a resin having a repeating unit represented by Formula (SP-2) and Formulae (SP-4) to (SP-6).
  • the structure of each repeating unit was determined from a 1 H-NMR spectrum.
  • the weight-average molecular weight (Mw) and the number-average molecular weight (Mn) of each resin are shown in the table below. In the following structures, the subscripts of the repeating units represent the content molar ratio of the respective repeating units.
  • reaction solution was cooled to 20° C. to 25° C., mixed with 300 mL of ethyl acetate, and transferred to a separatory funnel.
  • the mixture was washed twice with 300 mL of saturated aqueous sodium bicarbonate, washed with 300 mL of a saturated aqueous ammonium chloride solution, 300 mL of water, and 300 mL of saturated saline in this order, dried with sodium sulfate, 15 mg of p-methoxyphenol was added, the solvent was removed with an evaporator, and crystals of CX-1 was obtained.
  • CX-1 is a compound having a structure represented by Formula (CX-1).
  • reaction solution was cooled to 20° C. to 25° C., mixed with 800 mL of ethyl acetate, and transferred to a separatory funnel.
  • the mixture was washed twice with 300 mL of saturated aqueous sodium bicarbonate, washed with 300 mL of a saturated aqueous ammonium chloride solution, 300 mL of water, and 300 mL of saturated saline in this order, dried with sodium sulfate, 15 mg of p-methoxyphenol was added, the solvent was removed with an evaporator, and 13 g of CX-2 was obtained. It was confirmed by 1 H-NMR spectrum that the compound was CX-2.
  • CX-2 is a compound having a structure represented by Formula CX-2.
  • A-1 The weight-average molecular weight (Mw) of A-1 was 44,500, and the number-average molecular weight (Mn) thereof was 18,200. It was confirmed by 1 H-NMR spectrum that the structure of A-1 is a structure represented by Formula (A-1).
  • the obtained white solid was recovered and vacuum-dried at a temperature of 40° C. to obtain 71.8 g of A-2.
  • the weight-average molecular weight (Mw) of A-2 was 78,500, and the number-average molecular weight (Mn) thereof was 30,200. It was confirmed by 1 H-NMR spectrum that the structure of A-2 was a structure represented by Formula (A-2). From the measurement results of 1 H-NMR, the introduction rate of the crosslinking group was 55%.
  • 4,4′-(4,4′-isopropylidenediphenoxy)diphtalic acid anhydride (30.0 g (57.64 mmol)) was dissolved in 120 g of N-methylpyrrolidone (NMP) while removing moisture in a drying reactor comprising a bottom joint to which a stirrer, a condenser, and an internal thermometer were attached. Subsequently, 9.79 g (46.1 mmol) of m-triazine was dissolved in 80 g of NMP, and the solution was added dropwise thereto over 1 hour at a temperature of 10° C. to 25° C., stirred at 25° C.
  • NMP N-methylpyrrolidone
  • the weight-average molecular weight (Mw) of A-3 was 15,700, and the number-average molecular weight (Mn) thereof was 7,200. It was confirmed by 1 H-NMR spectrum that the structure of A-3 is a structure represented by Formula (A-3).
  • the content of each component described in the table was set to the amount (in terms of parts by mass) described in the column of “Adding amount” of each column of the table.
  • the obtained resin composition and comparative composition were subjected to pressure filtration using a filter made of a polypropylene having a micropore width of 0.5 km.
  • the description of “-” indicates that the corresponding component is not contained in the composition.
  • J-1 K-1 B B A A A B 6.7 1 Example — — — — 200° C. J-1 K-1 A A A A B 6.3 2

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